Metallocene compounds, catalysts comprising them, process for producing an olefin polymer by use of the catalysts, and olefin homo-and copolymers

ABSTRACT

Certain metallocene compounds are provided that, when used as a component in a supported polymerization catalyst under industrially relevant polymerization conditions, afford high molar mass homo polymers or copolymers like polypropylene or propylene/ethylene copolymers without the need for any α-branched substituent in either of the two available 2-positions of the indenyl ligands. The substituent in the 2-position of one indenyl ligand can be any radical comprising hydrogen, methyl, or any other C 2 -C 40  hydrocarbon which is not branched in the α-position, and the substituent in the 2-position of the other indenyl ligand can be any C 4 -C 40  hydrocarbon radical with the proviso that this hydrocarbon radical is branched in the β-position. This metallocene topology affords high melting point, very high molar mass homo polypropylene and very high molar mass propylene-based copolymers. The activity/productivity levels of catalysts including the metallocenes of the present invention are exceptionally high.

BACKGROUND

1. Field of the Invention

The present invention relates to novel metallocene compounds useful ascomponents in polymerization catalysts, to catalysts comprising suchmetallocene compounds, to a process for the polymerization of olefinsand to particularly propylene, and olefin homopolymers, random, andimpact copolymers prepared by using the metallocene catalysts.

2. Background of the Art

One of the most important factors determining the success of a catalystis its versatility, that is the possibility to use it for the broadestpossible range of products. For a long time, the limitations for thedevelopment of metallocene catalysts for polypropylene has been theirinability to produce propylene-ethylene copolymers of high molar mass,due to the fact that ethylene behaves as a chain transfer agent withmost metallocenes. This effect has been observed for all basicmetallocene structures, such as the syndiospecific C_(s) symmetricMe₂C(Cp)(Flu)ZrCl₂, the aspecific C_(2v) symmetric Me₂Si(Flu)₂ZrCl₂, andboth the C₂ symmetric rac-Me₂C(3-iPr-Ind)₂ZrCl₂ and the fluxional(2-Ph-Ind)₂ZrCl₂ catalysts for elastomeric polypropylene. This effecthas also been found for the isospecific C₂ symmetricrac-Me₂Si(2-Me-4,5-Benz-Ind)₂ZrCl₂ and rac-Me₂Si(2-Me-4-Ph-Ind)₂ZrCl₂[L. Resconi, C. Fritze, “Metallocene Catalysts for PropylenePolymerization” In Polypropylene Handbook (N. Pasquini, Ed.), ch. 2.2,Hanser Publishers, Munic 2005]. While the 2-Me substitution of thiscatalyst family suppresses the β-hydrogen transfer to the propylenemonomer and thus prevents the formation of low molar mass polymer, itfails to prevent the β-hydrogen transfer to the ethylene comonomer incase of the latter's presence. This β-hydrogen transfer to the ethylenecomonomer becomes the favored chain termination mechanism and leads tothe formation of low molar mass propylene-ethylene copolymers [A. Tynyset al., Macromol. Chem. Phys. 2005, vol. 206, pp. 1043-1056:“Ethylene-Propylene Copolymerizations: Effect of Metallocene Structureon Termination Reactions and Polymer Microstructure”]. Exceptions havebeen found in some zirconocenes with highly bulky ligands, such asrac-Me₂C(3-tBu-Ind)₂ZrCl₂, which show a marked increase in molar massesby ethylene incorporation. This catalyst, however, has shortcomings interms of homopolymer molar mass and activity.

Another key requirement of a metallocene catalyst is its capability toproduce polypropylene with a high melting point. This is equivalent witha catalyst that has a very high stereospecificity and regioselectivity.Within the rac-Alk₂Si(2-Alk-Ind)₂ZrCl₂ catalyst family, thestereospecificity and regioselectivity has continuously been improvedduring the last 15 years. EP-A1 834 519 relates to metallocenes of therac-Me₂Si(2-Me-4-Ar-Ind)₂ZrCl₂ for the production of high rigid, high Tmpolypropylenes with very high stereoregularity and very low amounts ofregio errors. Although not tested for their copolymerizationperformance, the metallocenes disclosed in EP-A1 834 519 anticipatedsubstitution patterns in 2-position that would later be identified asparticularly suitable for the production of propylene/ethylene randomcopolymers when combined with additional substituents in certainpositions. However, the highly stereo- and regio regular polypropyleneswere not obtained under commercially relevant process conditions andsuffered from too low activity/productivity levels.

US-A1 2001/0053833 discloses metallocenes having substituents in2-position consisting of an unsubstituted heteroaromatic ring or aheteroaromatic ring having at least one substituent bonded to the ring.Such catalysts afford C3/C2 copolymers with reasonably high molar mass,but fail to produce high Tm homopolymers under conditions typical forcommercial scale production, i.e. on a support and at temperatures from60 deg C. and higher. Also, the productivities of this catalyst familyare unsatisfactory.

WO 01/058970 relates to impact copolymers having a high melting pointand a high rubber molar mass, produced by catalysts comprisingmetallocenes of the rac-Me₂Si(2-Alk-4-Ar-Ind)₂ZrCl₂ family. High molarmasses in the propylene/ethylene rubber were achieved when both Alksubstituents were i-propyl groups. WO 02/002576 discloses bridgedmetallocenes of the (2-R-4-Ph-Ind)₂ZrCl₂ family having particularcombinations of substituents in the 2-positions of the indenyl ligandsand the Ph substituents. A high polypropylene (PP) melting point isfavored if the Ph group exhibits a substitution pattern in the 3 and 5positions, particularly in case of butyl substituents. A combination ofhigh homopolymer melting point and high copolymer molar mass is achievedif both substituents R in 2-position are isopropyl groups. The majorshortcoming is the very low activity/productivity of therac-Me₂Si(2-R-4-Ar-Ind)₂ZrCl₂ catalysts if both ligands R are branchedin the α-position. WO 03/002583 discloses bridged metallocenes of the(2-R-4-Ph-Ind)₂ZrCl₂ family having particular combinations ofsubstituents in the 2-positions of the indenyl ligands and the 4-Phsubstituents. A high PP melting point is favored if the Ph groupexhibits a substitution pattern in the 2-position, particularly in caseof biphenyl substituents. A combination of high homopolymer meltingpoint and high copolymer molar mass is achieved if both substituents Rin 2-position of the indenyl ligand are isopropyl groups. One majorshortcoming is the very low activity/productivity of therac-Me₂Si(2-R-4-Ar-Ind)₂ZrCl₂ catalysts if both ligands R are branchedin the α-position. Moreover, the highest possible molar masses of thehomopolymers produced by using such catalysts are relatively low whichcorresponds to relatively high melt flow rates. This, in turn excludessuch metallocenes from catering applications such as pipe, blown film,cast film and injection stretch blow molding.

EP-A2 1 250 365, WO 97/40075 and WO 03/045551 relate to metalloceneshaving substituents in the 2-positions of either of the indenyl ligandswith the imperative that at least one of the ligands in 2-position isbranched or cyclicized in the α-position. WO 04/106351 relates tometallocenes having substitutents in the 2-positions of the indenylligands with the proviso that one ligand is unbranched or bound via ansp²-hybridized carbon atom and the other ligand is branched in theα-position. Such catalysts afford high Tm homopolymers and high molarmass propylene/ethylene copolymers. However, there still are limitationswith regard to catalyst activity/productivity and lowest achievablehomopolymer melt flow rate.

In summary, the main deficiency of supported catalyst systems comprisingmetallocenes of the above mentioned prior art, is that so far nocatalyst has been found that, when used for the homopolymerization ofpropylene, affords isotactic polypropylene with a high melting point andvery high molar mass (or very low melt flow rate) and that, when usedfor the copolymerization of propylene with ethylene, affords high molarmass propylene/ethylene copolymers, all at very high catalystproductivity. As a consequence, when compared to Ziegler/Nattacatalysts, the industrial usefulness of these catalysts is limitedbecause certain applications that require a combination of a highmelting point, a very low melt flow rate, and/or a high molar masscopolymer or copolymer component, such as in impact copolymers, are notavailable at cost competitive productivities.

An object of the present invention is to address this shortcoming of thestate of the art metallocene compounds and to provide metallocenes thatincrease desirable characteristics such as high melting point, highmolar mass homopolymers and high molar mass copolymers, and do so athigher productivities when used as components of supported catalystsunder industrially relevant polymerization conditions at temperatures offrom 50° C. to 100° C. In addition, the inventions of the currentexample provide these advantages by using a Metallocene withsymmetrically substituted 2 positions on the indenyl group. This issignificantly more cost effective, and therefore far more desirable,than the comparative examples that have asymmetric substitution.

Another objective of the present invention is to provide a process forthe polymerization of olefins, particularly propylene, ethylene, andoptionally one or more higher 1-olefins.

Furthermore, it is an objective of the present invention to provideolefin polymers, particularly propylene homopolymers, random copolymersof propylene with ethylene and/or higher 1-olefins, impact copolymerscomprised of propylene, ethylene and/or optionally higher 1-olefins, andrandom impact copolymers comprised of propylene, ethylene and/oroptionally higher 1-olefins.

SUMMARY

Certain metallocene compounds are provided that, when used as acomponent in a supported polymerization catalyst under industriallyrelevant polymerization conditions, afford high molar mass homo polymersor copolymers like polypropylene or propylene/ethylene copolymerswithout the need for any α-branched substituent in either of the twoavailable 2-positions of the indenyl ligands. The substituent in the2-position of one indenyl ligand can be any radical comprising hydrogen,methyl, or any other C₂-C₄₀ hydrocarbon which is not branched in theα-position, and the substituent in the 2-position of the other indenylligand can be any C₄-C₄₀ hydrocarbon radical with the proviso that thishydrocarbon radical is branched in the β-position. This metallocenetopology affords high melting point, very high molar mass homopolypropylene and very high molar mass propylene-based copolymers.Furthermore, the activity/productivity levels of catalysts comprisingthe metallocenes of the present invention are exceptionally high.

While various metallocenes are described, for example, in U.S.Publication No. 2006/0116490, the improvement in olefin polymerizationachieved by the metallocene topology of the present invention is new andunexpected.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 illustrates individual steps of the process for producingtransition metal compounds of the bridged metallocene compound of theinvention.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT(S)

We have found that this object is achieved by a supported catalystsystem comprising at least one specifically substituted and bridgedmetallocene, at least one cocatalyst, at least one support and, ifdesired, at least one metal compound and further one additive component.According to the present invention, the catalyst system is prepared bymixing at least one specifically substituted and bridged metallocene, atleast one cocatalyst, at least one support and if desired at least onemetal compound and one further additive component.

The first embodiment of the invention relates to a substituted, bridgedmetallocene component of the general Formula 1 below,

where M¹ is a metal of Group IVb of the Periodic Table of the Elements,preferably Zirconium or Hafnium, and particularly preferably Zirconium.

R¹ and R² are identical or different and are each a hydrogen atom, analkyl group of from 1 to about 10 carbon atoms, an alkoxy group of from1 to about 10 carbon atoms, an aryl group of from 6 to about 20 carbonatoms, an aryloxy group of from 6 to about 10 carbon atoms, an alkenylgroup of from 2 to about 10 carbon atoms, an OH group, a halogen atom,or a NR₂ ³² group, where R³² is an alkyl group of from 1 to about 10carbon atoms or an aryl group of from 6 to about 14 carbon atoms and R¹and R² may form one or more ring system(s). Preferably, R¹ and R² areidentical or different and are an alkyl group of from 1 to about 10carbon atoms, an alkoxy group of from 1 to about 10 carbon atoms, anaryloxy group of from 6 to about 10 carbon atoms or a halogen atom, orR¹ and R² together may form one or more ring system(s). Particularlypreferably, R¹ and R² are identical or different and are methyl,chlorine or phenolate.

R⁴ and R^(4′) are identical or different and are each a hydrogen atom, alinear, cyclic or branched hydrocarbon group, for example an alkyl groupof from 1 to 20 carbon atoms, an alkenyl group of from 2 to 20 carbonatoms, an aryl group of from 6 to 20 carbon atoms, an arylalkyl group offrom 7 to 40 carbon atoms, an alkylaryl group of from 8 to about 40carbon atoms, or an arylalkenyl group of from 8 to about 40 carbon atomsor a substituted or unsubstituted alkylsilyl group, an alkyl(aryl)silylgroup or an arylsilyl group. The group may contain one or more heteroatoms like Si, B, Al, O, S, N or P, and/or may contain halogen atomslike F, Cl or Br. Preferably, R⁴ and R^(4′) are identical or differentand, are each a hydrogen atom, a linear, cyclic or branched hydrocarbongroup, for example an alkyl group of from 1 to about 10 carbon atoms, analkenyl group of from 2 to about 10 carbon atoms, an aryl group of from6 to about 10 carbon atoms, an arylalkyl group of from 7 to about 20carbon atoms, an alkylaryl group of from 8 to about 20 carbon atoms, oran arylalkenyl group of from 8 to about 20 carbon atoms or a substitutedor unsubstituted alkylsilyl group, an alkyl(aryl)silyl group or anarylsilyl group. The groups may be halogenated. Particularly preferably,R⁴ and R^(4′) are both hydrogen.

R¹⁰ is a bridging group wherein R¹⁰ is selected from:

where

R⁴⁰ and R⁴¹, even when bearing the same index, can be identical ordifferent and are each a hydrogen atom, a C₁-C₄₀ group such as an alkylgroup having from 1 to about 30 carbon atoms, an aryl group of from 6 toabout 40 carbon atoms, a fluoroalkyl group of from 1 to about 10 carbonatoms, an alkoxy group of from 1 to about 10 carbon atoms, an aryloxygroup of from 6 to about 10 carbon atoms, an alkenyl group of from 2 toabout 10 carbon atoms, an arylalkyl group of from 7 to about 40 carbonatoms, an alkylaryl group of from 7 to about 40 carbon atoms, asubstituted or unsubstituted alkylsilyl, alkyl(aryl)silyl or arylsilylgroup, or an arylalkenyl group of from 8 to about 40 carbon atoms. R⁴⁰and R⁴¹ together with the atoms connecting them can form one or morecyclic systems or R⁴⁰ and/or R⁴¹ can contain additional hetero atoms(i.e., non-carbon atoms) like Si, B, Al, O, S, N or P or halogen atomslike Cl or Br,

x is an integer from 1 to 18,

M¹² is silicon, germanium or tin, and

R¹⁰ may also link two units of the formula 1 to one another,

Preferably, R¹⁰ is R⁴⁰R⁴¹Si═, R⁴⁰R⁴¹Ge═, R⁴⁰R⁴¹C═ or—(R⁴⁰R⁴¹C—CR⁴⁰R⁴¹)—, where R⁴⁰ and R⁴¹ are identical or different andare each a hydrogen atom, a hydrocarbon group of from 1 to about 30carbon atoms, in particular an alkyl group of from 1 to about 10 carbonatoms, an aryl group of from 6 to about 40 carbon atoms, an arylalkylgroup of from 7 to about 14 carbon atoms, an alkylaryl group of from 7to about 14 carbon atoms or a substituted or unsubstituted alkylsilylgroup, an alkyl(aryl)silyl or an arylsilyl group.

Particularly preferably, the bridging unit R¹⁰ is R⁴⁰R⁴¹Si═ orR⁴⁰R⁴¹Ge═, where R⁴⁰ and R⁴¹ are identical or different and are methyl,ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl,undecyl, dodecyl, cyclopentyl, cyclopentadienyl, cyclohexyl, phenyl,naphthyl, benzyl, trimethylsilyl or 3,3,3-trifluoropropyl.

R¹¹ and R^(11′) are identical or different and are each a divalentC₂-C₄₀ group which together with the cyclopentadienyl ring forms afurther saturated or unsaturated ring system having a ring size of from5 to 7 atoms, where R¹¹ and R^(11′) may contain the heteroatoms Si, Ge,N, P, O or S within the ring system fused onto the cyclopentadienylring. Preferably, the groups R¹¹ and R^(11′) are identical or differentand are each a divalent group selected from those given in Formulae 1 α,β, γ, δ, φ, and ν and Formulae 1 α′, β′, γ′, δ′, φ′, and ν′,respectively. The asterisks “*” and “**” in Formula 1 and Formulae 1 α-νand 1 α′-ν′, respectively, denote the chemical bonds joining R¹¹ andR^(11′) to the cyclopentadienyl rings. For illustration, if R¹¹ isrepresented by Formula 1γ and R^(11′) is represented by Formula 1γ′,then the structure given in Formula 1a (see below) is obtained.Particularly preferably, R¹¹ and R^(11′) are identical or different andR¹¹ is a divalent group according to Formula 1γ and R^(11′) is selectedfrom the divalent groups in Formulae 1α′, β′, and γ′ or R¹¹ and R^(11′)are identical or different and are divalent groups according to Formula1α and 1α′ or Formula 1β and 1β′ or Formula 1γ and 1γ′ or Formula 1δ and1δ′ or Formula 1φ and 1φ′ or Formula 1ν and 1ν′, respectively.

R⁵, R⁶, R⁷, R⁸, and R⁹ and also R^(5′), R^(6′), R^(7′), R^(8′) andR^(9′) as well as R⁵⁵, R⁶⁶, R⁷⁷, R⁸⁸ and R⁹⁹ and also R^(55′), R^(66′),R^(77′), R^(88′) and R^(99′) are identical or different and are each ahydrogen atom, a linear, cyclic or branched hydrocarbon group, forexample an alkyl group of from 2 to about 20 carbon atoms, an alkenylgroup of from 2 to about 20 carbon atoms, an aryl group of from 6 toabout 40 carbon atoms, an arylalkyl group of from 7 to about 40 carbonatoms, an alkylaryl group of from 7 to about 40 carbon atoms, or anarylalkenyl group of from 8 to about 40 carbon atoms or a substituted orunsubstituted alkylsilyl group, an alkyl(aryl)silyl group or anarylsilyl group. Two adjacent radicals R⁵, R⁶ or R^(5′), R^(6′) or R⁶,R⁷ or R^(6′), R^(7′) or R⁷, R⁸ or R^(7′), R^(8′) or R⁸, R⁹ or R^(8′),R^(9′) as well as R⁵⁵, R⁶⁶ or R^(55′), R^(66′) or R⁶⁶, R⁷⁷ or R^(66′),R^(77′) or R⁷⁷, R⁸⁸ or R^(77′), R^(88′) or R⁸⁸, R⁹⁹ or R^(88′), R^(99′)in each case may form a saturated or unsaturated hydrocarbon ringsystem. The groups may contain one or more hetero atoms like Si, B, Al,O, S, N or P, and/or may contain halogen atoms like F, Cl or Br.

Preferably, R⁵⁵, R⁶⁶, R⁷⁷, R⁸⁸ and R⁹⁹ and also R^(55′), R^(66′),R^(77′), R^(88′) and R^(99′) are each a hydrogen atom and R⁵, R⁶, R⁷, R⁸and R⁹ and also R^(5′), R^(6′), R^(7′), R^(8′) and R^(9′) are identicalor different and are each a hydrogen atom, a substituted orunsubstituted alkylsilyl or arylsilyl group, a linear, cyclic orbranched alkyl group of from 1 to about 10 carbon atoms, or an arylgroup of from 6 to about 40 carbon atoms and the groups may contain oneor more hetero atoms like Si, B, Al, O, S, N or P, and/or may containhalogen atoms like F, Cl or Br. The two adjacent radicals R⁵/R⁶ and alsoR^(5′)/R^(6′) may form a hydrocarbon ring system or R⁵ and R^(5′) areidentical or different and are each a substituted or unsubstituted arylgroup of from 6 to about 40 carbon atoms.

Particularly preferably, R⁵⁵, R⁶⁶, R⁷⁷, R⁸⁸ and R⁹⁹ and also R^(55′),R^(66′), R^(77′), R^(88′) and R^(99′) are each a hydrogen atom and R⁵,R⁶, R⁷, R⁸ and R⁹ and also R^(5′), R^(6′), R^(7′), R^(8′) and R^(9′) areidentical or different and are each a hydrogen atom or a linear, cyclicor branched alkyl group of from 1 to about 10 carbon atoms, or an arylgroup of from 6 to about 40 carbon atoms. The two adjacent radicals R⁵,R⁶ and also R^(5′), R^(6′) together may form a ring system or R⁵ andR^(5′) are identical or different and are each a substituted orunsubstituted aryl group of from 6 to about 40 carbon atoms.

R³⁰⁰ is a —CH₂—CR³⁰¹R³⁰²R³⁰³ or a —CH═CR³⁰²R³⁰³ group, where R³⁰¹, R³⁰²and R³⁰³ are identical or different and/or R³⁰² and R³⁰³ together mayform a ring system and/or R³⁰¹, R³⁰² and R³⁰³ together may form a ringsystem, and R³⁰¹, R³⁰², R³⁰³ are each a hydrogen atom, a linear, cyclicor branched hydrocarbon group, for example an alkyl group of from 1 toabout 20 carbon atoms, an alkenyl group of from 2 to about 20 carbonatoms, an aryl group of from 6 to about 20 carbon atoms, an arylalkylgroup of from 7 to about 40 carbon atoms, an alkylaryl group of from 7to about 40 carbon atoms, or an arylalkenyl group of from 8 to about 40carbon atoms, an alkoxy group of from 1 to about 20 carbon atoms, anaryloxy group of from 6 to about 20 carbon atoms, or a substituted orunsubstituted alkylsilyl group, an alkyl(aryl)silyl group or anarylsilyl group, and the groups may contain one or more hetero atomslike Si, B, Al, O, S, N or P, and/or may contain halogen atoms like F,Cl or Br, with the proviso, that R³⁰² and R³⁰³ are not a hydrogen atom.

Preferably, R³⁰⁰ is a —CH₂—CR³⁰¹R³⁰²R³⁰³ group, where R³⁰¹, R³⁰² andR³⁰³ are identical or different and/or R³⁰² and R³⁰³ together may form aring system and/or R³⁰¹, R³⁰² and R³⁰³ together may form a ring system,and R³⁰¹, R³⁰², R³⁰³ are each a hydrogen atom, a linear, cyclic orbranched hydrocarbon group which may be halogenated, for example analkyl group of from 1 to about 20 carbon atoms, an alkenyl group of from2 to about 20 carbon atoms, an aryl group of from 6 to about 20 carbonatoms, an arylalkyl group of from 7 to about 40 carbon atoms, analkylaryl group of from 7 to about 40 carbon atoms, an arylalkenyl groupof from 8 to about 40 carbon atoms, an alkoxy group of from 1 to about10 carbon atoms or an aryloxy group of from 6 to about 20 carbon atoms,with the proviso, that R³⁰² and R³⁰³ are not a hydrogen atom.

Particularly preferably, R³⁰⁰ is a —CH₂—CR³⁰¹R³⁰²R³⁰³ group, where R³⁰¹is a hydrogen atom and where R³⁰² and R³⁰³ are identical or differentand/or R³⁰² and R³⁰³ together may form a ring system, and R³⁰² and R³⁰³are each a linear, cyclic or branched hydrocarbon group which may behalogenated, for example an alkyl group of from 1 to about 10 carbonatoms, an alkenyl group of from 2 to about 10 carbon atoms, an arylgroup of from 6 to about 10 carbon atoms, an arylalkyl group of from 7to about 20 carbon atoms, an alkylaryl group of from 7 to about 20carbon atoms, an arylalkenyl group of from 8 to about 20 carbon atoms,an alkoxy group of from 1 to about 10 carbon atoms, or an aryloxy groupof from 6 to about 20 carbon atoms, with the proviso, that R³⁰⁰ containsmore than 6 carbon atoms.

Most preferably, R³⁰⁰ is a —CH₂—CR³⁰¹R³⁰²R³⁰³ group, where R³⁰¹ and R³⁰²and R³⁰³ are identical or different and/or R³⁰² and R³⁰³ together mayform a ring system, and/or R³⁰¹, R³⁰² and R³⁰³ together may form a ringsystem, and R³⁰¹, R³⁰², R³⁰³ are each a linear, cyclic or branchedhydrocarbon group which may be halogenated, for example an alkyl groupof from 1 to about 10 carbon atoms, an alkenyl group of from 2 to about10 carbon atoms, an aryl group of from 6 to about 10 carbon atoms, anarylalkyl group of from 7 to about 20 carbon atoms, an alkylaryl groupof from 7 to about 20 carbon atoms, an arylalkenyl group of from 8 toabout 20 carbon atoms, an alkoxy group of from 1 to about 10 carbonatoms or an aryloxy group of from 6 to about 20 carbon atoms, with theproviso, that R³⁰⁰ contains more than 6 carbon atoms.

R³ has the meaning of R³⁰⁰ (but need not be identical to R³⁰⁰) or R³ isa hydrogen atom, a linear, cyclic or branched hydrocarbon group whichmay be halogenated and/or may contain one or more hetero atoms like Si,B, Al, O, S, N or P, for example an alkyl group of from 1 to about 20carbon atoms, an alkylalkenyl group of from 3 to about 20 carbon atoms,an alkylaryl group of from 7 to about 40 carbon atoms, or analkylarylalkenyl group of from 9 to about 40 carbon atoms, with theproviso that R³ is not cyclic or branched in α-position.

Preferably, R³ has the meaning of R³⁰⁰ (but need not be identical toR³⁰⁰) or R³ is a linear, cyclic or branched hydrocarbon group of from 1to about 20 carbon atoms, for example an alkyl group of from 1 to 20carbon atoms, an alkylaryl group of from 7 to about 20 carbon atoms, analkylalkenyl group of from 3 to about 20 carbon atoms or analkylarylalkenyl group of from 9 to about 20 carbon atoms with theproviso that R³ is not cyclic or branched in α-position.

More preferably, R³ and R³⁰⁰ are identical or R³ is a methyl group or alinear, cyclic or branched hydrocarbon group of from 7 to about 10carbon atoms which may be halogenated, an alkylaryl group of from 7 toabout 10 carbon atoms or an alkylalkenyl group of from 7 to about 10carbon atoms with the proviso that R³ is not cyclic or branched inα-position.

Particularly preferably, R³ and R³⁰⁰ are identical and are a—CH₂—CR³⁰¹R³⁰²R³⁰³ group, where R³⁰¹, R³⁰² and R³⁰³ are identical ordifferent and/or R³⁰² and R³⁰³ together may form a ring system, and/orR³⁰¹, R³⁰² and R³⁰³ together may form a ring system, and are each ahydrogen atom, a linear, cyclic or branched hydrocarbon group which maybe halogenated, for example an alkyl group of from 1 to about 20 carbonatoms, an alkenyl group of from 2 to about 20 carbon atoms, an arylgroup of from 6 to about 20 carbon atoms, an arylalkyl group of from 7to about 40 carbon atoms, an alkylaryl group of from 7 to about 40carbon atoms, an arylalkenyl group of from 8 to about 40 carbon atoms,an alkoxy group of from 1 to about 10 carbon atoms, or an aryloxy groupof from 6 to about 20 carbon atoms, with the proviso, that no more thanone of R³⁰¹, R³⁰² and R³⁰³ are a hydrogen atom.

More particularly preferably, R³ and R³⁰⁰ are identical and are a—CH₂—CR³⁰¹R³⁰²R³⁰³ group, where R³⁰³ is a hydrogen atom and where R³⁰¹and R³⁰² are identical or different and/or R³⁰² and R³⁰³ together mayform a ring system, and are each a linear, cyclic or branchedhydrocarbon group which may be halogenated, for example an alkyl groupof from 1 to about 10 carbon atoms, an alkenyl group of from 2 to about10 carbon atoms, an arylalkyl group of from 7 to about 20 carbon atoms,an alkylaryl group of from 7 to about 20 carbon atoms, an arylalkenylgroup of from 8 to about 20 carbon atoms, an alkoxy group of from 1 toabout 10 carbon atoms, or an aryloxy group of from 6 to about 20 carbonatoms, with the proviso that R³ and R³⁰⁰ contain more than 6 carbonatoms.

Most preferably, R³ and R³⁰⁰ are identical and are a —CH₂—CR³⁰¹R³⁰²R³⁰³group, where R³⁰³ and R³⁰¹ and R³⁰² are identical or different and/orR³⁰² and R³⁰³ together may form a ring system, and/or R³⁰¹, R³⁰² andR³⁰³ together may form a ring system, and are each a linear, cyclic orbranched hydrocarbon group which may be halogenated, for example analkyl group of from 1 to about 10 carbon atoms, an alkenyl group of from2 to about 10 carbon atoms, an arylalkyl group of from 7 to about 20carbon atoms, an alkylaryl group of from 7 to about 20 carbon atoms, anarylalkenyl group of from 8 to about 20 carbon atoms, an alkoxy group offrom 1 to about 10 carbon atoms, or an aryloxy group of from 6 to about20 carbon atoms, with the proviso that R³ and R³⁰⁰ contain more than 6carbon atoms.

Preferably, the specifically substituted, bridged metallocene componentof the first embodiment of the invention is as given in Formula 1abelow.

M¹, R¹, R², R³, R⁴, R^(4′), R¹⁰ and R³⁰⁰ have the meaning set forthabove with respect to Formula 1.

For the substituents R⁵, R⁶, R⁷ and R⁸ and also R^(5′), R^(6′), R^(7′)and R^(8′) of Formula 1a, there are two equitable substitution patterns.

In the first substitution pattern, R⁵, R⁶, R⁷ and R⁸ and also R^(5′),R^(6′), R^(7′) and R^(8′) are identical or different and are each ahydrogen atom, a linear, cyclic or branched hydrocarbon group, forexample an alkyl group of from 1 to about 20 carbon atoms, an alkenylgroup of from 2 to about 20 carbon atoms, an aryl group of from 6 toabout 40 carbon atoms, an arylalkyl group of from 7 to about 40 carbonatoms, an alkylaryl group of from 7 to about 40 carbon atoms, or anarylalkenyl group of from 8 to about 40 carbon atoms or a substituted orunsubstituted alkylsilyl group, an alkyl(aryl)silyl group or anarylsilyl group. The groups may contain one or more hetero atoms likeSi, B, Al, O, S, N or P, and/or may contain halogen atoms like F, Cl orBr, and/or two adjacent radicals R⁵, R⁶ or R⁶, R⁷ or R⁷, R⁸ and alsoR^(5′), R^(6′) or R^(6′), R^(7′) or R^(7′), R^(8′) in each case may forma hydrocarbon ring system.

Preferably, R⁵, R⁶, R⁷ and R⁸ and also R^(5′), R^(6′), R^(7′) and R^(8′)are identical or different and are each a hydrogen atom, a substitutedor unsubstituted alkylsilyl or arylsilyl group, a linear, cyclic orbranched alkyl group of from 1 to about 10 carbon atoms, or an arylgroup of from 6 to about 40 carbon atoms, which may contain one or morehetero atoms like Si, B, Al, O, S, N or P, and/or may contain halogenatoms like F, Cl or Br, and/or the two adjacent radicals R⁵, R⁶ and alsoR^(5′), R^(6′) may form a saturated or unsaturated hydrocarbon ringsystem.

Particularly preferably, R⁵, R⁶, R⁷ and R⁸ and also R^(5′), R^(6′),R^(7′) and R^(8′) are identical or different and are each a hydrogenatom or a linear, cyclic or branched alkyl group of from 1 to about 10carbon atoms, or an aryl group of from 6 to about 40 carbon atoms and/orthe two adjacent radicals R⁵, R⁶ and also R^(5′), R^(6′) together mayform a saturated or unsaturated ring system.

In the second substitution pattern, R⁶, R⁷, R⁸ and also R^(6′), R^(7′)and R^(8′) are identical or different and are each a hydrogen atom, alinear, cyclic or branched hydrocarbon group, for example an alkyl groupof from 1 to about 10 carbon atoms, an alkenyl group of from 2 to about10 carbon atoms, an aryl group of from 6 to about 20 carbon atoms, anarylalkyl group of from 7 to about 40 carbon atoms, an alkylaryl groupof from 7 to about 40 carbon atoms, or an arylalkenyl group of from 8 toabout 40 carbon atoms or a substituted or unsubstituted alkylsilylgroup, an alkyl(aryl)silyl group or an arylsilyl group. Two adjacentradicals R⁶, R⁷ or R⁷, R⁸ as well as R^(6′), R^(7′) or R^(7′), R^(8′) ineach case may form a hydrocarbon ring system. The groups may contain oneor more hetero atoms like Si, B, Al, O, S, N or P, and/or may containhalogen atoms like F, Cl or Br. R⁵ and R^(5′) are identical or differentand are each a substituted or unsubstituted aryl group of from 6 toabout 40 carbon atoms. They may contain one or more hetero atoms likeSi, B, Al, O, S, N or P, and/or may contain halogen atoms like F, Cl orBr.

Preferably, R⁶, R⁷ and R⁸ and also R^(6′), R^(7′) and R^(8′) areidentical or different and are each a hydrogen atom, a substituted orunsubstituted alkylsilyl or arylsilyl group, a linear, cyclic orbranched alkyl group of from 1 to about 10 carbon atoms, or an arylgroup of from 6 to about 10 carbon atoms, which may contain one or morehetero atoms like Si, B, Al, O, S, N or P, and/or may contain halogenatoms like F, Cl or Br. R⁵ and R^(5′) are identical or different and areeach a substituted or unsubstituted aryl group of from 6 to about 40carbon atoms.

Particularly preferably, R⁶, R⁷ and R⁸ and also R^(6′), R^(7′) andR^(8′) are identical or different and are each a hydrogen atom or alinear, cyclic or branched alkyl group of from 1 to about 10 carbonatoms, or an aryl group of from 6 to about 10 carbon atoms. R⁵ andR^(5′) are identical or different and are each naphthyl,4-(C₁-C₁₀-alkyl)phenyl or 4-(C₆-C₂₀-aryl)phenyl such as 4-methyl-phenyl,4-biphenyl, 4-ethyl-phenyl, 4-n-propyl-phenyl, 4-isopropyl-phenyl,4-tert-butyl-phenyl, 4-sec-butyl-phenyl, 4-cyclohexyl-phenyl,4-trimethylsilyl-phenyl, 4-adamantyl-phenyl,4-(C₁-C₁₀-fluoroalkyl)-phenyl, 3-(C₁-C₁₀-alkyl)-phenyl,3-(C₁-C₁₀-fluoroalkyl)-phenyl, 3-(C₆-C₂₀-aryl)phenyl like 3-biphenyl,3,5-di-(C₁-C₁₀-alkyl)-phenyl such as 3,5-dimethyl-phenyl,3,5-di-(C₁-C₁₀-fluoroalkyl)-phenyl, such as3,5-di(trifluoromethyl)-phenyl or 3,5-(C₆-C₂₀-aryl)phenyl like3,5-terphenyl.

Non-limiting examples for the very particularly preferred metallocenecompounds according to Formula 1 and 1a are given below:

-   Dimethylsilanediylbis[2-t-butylmethyl-4-(1-naphthyl)-indenyl]zirconiumdichloride;-   Dimethylsilanediylbis[2-t-butylmethyl-4-(2-naphthyl)-indenyl]zirconiumdichloride;-   Dimethylsilanediylbis[2-t-butylmethyl-4-(4-methyl-phenyl)-indenyl]zirconiumdichloride;-   Dimethylsilanediylbis[2-t-butylmethyl-4-(4-biphenyl)-indenyl]zirconiumdichloride;-   Dimethylsilanediylbis[2-t-butylmethyl-4-(4-ethyl-phenyl)-indenyl]zirconiumdichloride;-   Dimethylsilanediylbis[2-t-butylmethyl-4-(4-n-propyl-phenyl)-indenyl]zirconiumdichloride;-   Dimethylsilanediylbis[2-t-butylmethyl-4-(4-i-propyl-phenyl)-indenyl]zirconiumdichloride;-   Dimethylsilanediylbis[2-t-butylmethyl-4-(4-t-butyl-phenyl)-indenyl]zirconiumdichloride;-   Dimethylsilanediylbis[2-t-butylmethyl-4-(4-sec-butyl-phenyl)-indenyl]zirconiumdichloride;-   Dimethylsilanediylbis[2-t-butylmethyl-4-(4-cyclohexyl-phenyl)-indenyl]zirconiumdichloride;-   Dimethylsilanediylbis[2-t-butylmethyl-4-(4-trimethylsilyl-phenyl)-indenyl]zirconiumdichloride;-   Dimethylsilanediylbis[2-t-butylmethyl-4-(4-adamantyl-phenyl)-indenyl]zirconiumdichloride;-   Dimethylsilanediylbis[2-t-butylmethyl-4-(3-biphenyl)-indenyl]zirconiumdichloride;-   Dimethylsilanediylbis[2-t-butylmethyl-4-(3,5-dimethyl-phenyl)-indenyl]zirconiumdichloride;-   Dimethylsilanediylbis[2-t-butylmethyl-4-(3,5-di-(trifluoromethyl)-phenyl)-indenyl]zirconiumdichloride;-   Dimethylsilanediylbis[2-t-butylmethyl-4-(3,5-terphenyl)-indenyl]zirconiumdichloride;-   Dimethylsilanediylbis[2-cyclopentylmethyl-4-(1-naphthyl)-indenyl]zirconiumdichloride;-   Dimethylsilanediylbis[2-cyclopentylmethyl-4-(2-naphthyl)-indenyl]zirconiumdichloride;-   Dimethylsilanediylbis[2-cyclopentylmethyl-4-(4-methyl-phenyl)-indenyl]zirconiumdichloride;-   Dimethylsilanediylbis[2-cyclopentylmethyl-4-(4-biphenyl)-indenyl]zirconiumdichloride;-   Dimethylsilanediylbis[2-cyclopentylmethyl-4-(4-ethyl-phenyl)-indenyl]zirconiumdichloride;-   Dimethylsilanediylbis[2-cyclopentylmethyl-4-(4-n-propyl-phenyl)-indenyl]zirconiumdichloride;-   Dimethylsilanediylbis[2-cyclopentylmethyl-4-(4-i-propyl-phenyl)-indenyl]zirconiumdichloride;-   Dimethylsilanediylbis[2-cyclopentylmethyl-4-(4-t-butyl-phenyl)-indenyl]zirconiumdichloride;-   Dimethylsilanediylbis[2-cyclopentylmethyl-4-(4-sec-butyl-phenyl)-indenyl]zirconiumdichloride;-   Dimethylsilanediylbis[2-cyclopentylmethyl-4-(4-cyclohexyl-phenyl)-indenyl]zirconiumdichloride;-   Dimethylsilanediylbis[2-cyclopentylmethyl-4-(4-trimethylsilyl-phenyl)-indenyl]zirconiumdichloride;-   Dimethylsilanediylbis[2-cyclopentylmethyl-4-(4-adamantyl-phenyl)-indenyl]zirconiumdichloride;-   Dimethylsilanediylbis[2-cyclopentylmethyl-4-(3-biphenyl)-indenyl]zirconiumdichloride;-   Dimethylsilanediylbis[2-cyclopentylmethyl-4-(3,5-dimethyl-phenyl)-indenyl]zirconiumdichloride;-   Dimethylsilanediylbis[2-cyclopentylmethyl-4-(3,5-di-(trifluoromethyl)-phenyl)-indenyl]zirconiumdichloride;-   Dimethylsilanediylbis[2-cyclopentylmethyl-4-(3,5-terphenyl)-indenyl]zirconiumdichloride;-   Dimethylsilanediylbis[2-cyclohexylmethyl-4-(1-naphthyl)-indenyl]zirconiumdichloride;-   Dimethylsilanediylbis[2-cyclohexylmethyl-4-(2-naphthyl)-indenyl]zirconiumdichloride;-   Dimethylsilanediylbis[2-cyclohexylmethyl-4-(4-methyl-phenyl)-indenyl]zirconiumdichloride;-   Dimethylsilanediylbis[2-cyclohexylmethyl-4-(4-biphenyl)-indenyl]zirconiumdichloride;-   Dimethylsilanediylbis[2-cyclohexylmethyl-4-(4-ethyl-phenyl)-indenyl]zirconiumdichloride;-   Dimethylsilanediylbis[2-cyclohexylmethyl-4-(4-n-propyl-phenyl)-indenyl]zirconiumdichloride;-   Dimethylsilanediylbis[2-cyclohexylmethyl-4-(4-i-propyl-phenyl)-indenyl]zirconiumdichloride;-   Dimethylsilanediylbis[2-cyclohexylmethyl-4-(4-t-butyl-phenyl)-indenyl]zirconiumdichloride;-   Dimethylsilanediylbis[2-cyclohexylmethyl-4-(4-sec-butyl-phenyl)-indenyl]zirconiumdichloride;-   Dimethylsilanediylbis[2-cyclohexylmethyl-4-(4-cyclohexyl-phenyl)-indenyl]zirconiumdichloride;-   Dimethylsilanediylbis[2-cyclohexylmethyl-4-(4-trimethylsilyl-phenyl)-indenyl]zirconiumdichloride;-   Dimethylsilanediylbis[2-cyclohexylmethyl-4-(4-adamantyl-phenyl)-indenyl]zirconiumdichloride;-   Dimethylsilanediylbis[2-cyclohexylmethyl-4-(3-biphenyl)-indenyl]zirconiumdichloride;-   Dimethylsilanediylbis[2-cyclohexylmethyl-4-(3,5-dimethyl-phenyl)-indenyl]zirconiumdichloride;-   Dimethylsilanediylbis[2-cyclohexylmethyl-4-(3,5-di-(trifluoromethyl)-phenyl)-indenyl]zirconiumdichloride;-   Dimethylsilanediylbis[2-cyclohexylmethyl-4-(3,5-terphenyl)-indenyl]zirconiumdichloride;-   Dimethylsilanediylbis[2-cycloheptylmethyl-4-(1-naphthyl)-indenyl]zirconiumdichloride;-   Dimethylsilanediylbis[2-cycloheptylmethyl-4-(2-naphthyl)-indenyl]zirconiumdichloride;-   Dimethylsilanediylbis[2-cycloheptylmethyl-4-(4-methyl-phenyl)-indenyl]zirconiumdichloride;-   Dimethylsilanediylbis[2-cycloheptylmethyl-4-(4-biphenyl)-indenyl]zirconiumdichloride;-   Dimethylsilanediylbis[2-cycloheptylmethyl-4-(4-ethyl-phenyl)-indenyl]zirconiumdichloride;-   Dimethylsilanediylbis[2-cycloheptylmethyl-4-(4-n-propyl-phenyl)-indenyl]zirconiumdichloride;-   Dimethylsilanediylbis[2-cycloheptylmethyl-4-(4-i-propyl-phenyl)-indenyl]zirconiumdichloride;-   Dimethylsilanediylbis[2-cycloheptylmethyl-4-(4-t-butyl-phenyl)-indenyl]zirconiumdichloride;-   Dimethylsilanediylbis[2-cycloheptylmethyl-4-(4-sec-butyl-phenyl)-indenyl]zirconiumdichloride;-   Dimethylsilanediylbis[2-cycloheptylmethyl-4-(4-cyclohexyl-phenyl)-indenyl]zirconiumdichloride;-   Dimethylsilanediylbis[2-cycloheptylmethyl-4-(4-trimethylsilyl-phenyl)-indenyl]zirconiumdichloride;-   Dimethylsilanediylbis[2-cycloheptylmethyl-4-(4-adamantyl-phenyl)-indenyl]zirconiumdichloride;-   Dimethylsilanediylbis[2-cycloheptylmethyl-4-(3-biphenyl)-indenyl]zirconiumdichloride;-   Dimethylsilanediylbis[2-cycloheptylmethyl-4-(3,5-dimethyl-phenyl)-indenyl]zirconiumdichloride;-   Dimethylsilanediylbis[2-cycloheptylmethyl-4-(3,5-di-(trifluoromethyl)-phenyl)-indenyl]zirconiumdichloride;-   Dimethylsilanediylbis[2-cycloheptylmethyl-4-(3,5-terphenyl)-indenyl]zirconiumdichloride;-   Dimethylsilanediylbis[2-adamantylmethyl-4-(1-naphthyl)-indenyl]zirconiumdichloride;-   Dimethylsilanediylbis[2-adamantylmethyl-4-(2-naphthyl)-indenyl]zirconiumdichloride;-   Dimethylsilanediylbis[2-adamantylmethyl-4-(4-methyl-phenyl)-indenyl]zirconiumdichloride;-   Dimethylsilanediylbis[2-adamantylmethyl-4-(4-biphenyl)-indenyl]zirconiumdichloride;-   Dimethylsilanediylbis[2-adamantylmethyl-4-(4-ethyl-phenyl)-indenyl]zirconiumdichloride;-   Dimethylsilanediylbis[2-adamantylmethyl-4-(4-n-propyl-phenyl)-indenyl]zirconiumdichloride;-   Dimethylsilanediylbis[2-adamantylmethyl-4-(4-i-propyl-phenyl)-indenyl]zirconiumdichloride;-   Dimethylsilanediylbis[2-adamantylmethyl-4-(4-t-butyl-phenyl)-indenyl]zirconiumdichloride;-   Dimethylsilanediylbis[2-adamantylmethyl-4-(4-sec-butyl-phenyl)-indenyl]zirconiumdichloride;-   Dimethylsilanediylbis[2-adamantylmethyl-4-(4-cyclohexyl-phenyl)-indenyl]zirconiumdichloride;-   Dimethylsilanediylbis[2-adamantylmethyl-4-(4-trimethylsilyl-phenyl)-indenyl]zirconiumdichloride;-   Dimethylsilanediylbis[2-adamantylmethyl-4-(4-adamantyl-phenyl)-indenyl]zirconiumdichloride;-   Dimethylsilanediylbis[2-adamantylmethyl-4-(3-biphenyl)-indenyl]zirconiumdichloride;-   Dimethylsilanediylbis[2-adamantylmethyl-4-(3,5-dimethyl-phenyl)-indenyl]zirconiumdichloride;-   Dimethylsilanediylbis[2-adamantylmethyl-4-(3,5-di-(trifluoromethyl)-phenyl)-indenyl]zirconiumdichloride;-   Dimethylsilanediylbis[2-adamantylmethyl-4-(3,5-terphenyl)-indenyl]zirconiumdichloride;-   Dimethylsilanediylbis[2-trimethylsilylmethyl-4-(4-t-butyl-phenyl)-indenyl]zirconiumdichloride;-   Dimethylsilanediylbis[2-(2-methoxy-2-methyl-propyl)-4-(4-t-butyl-phenyl)-indenyl]zirconiumdichloride;-   Dimethylsilanediylbis[2-(2,6-dimethyl-benzyl)-4-(4-t-butyl-phenyl)-indenyl]zirconiumdichloride;-   Dimethylsilanediylbis[2-(2,4,6-trimethyl-benzyl)-4-(4-t-butyl-phenyl)-indenyl]zirconiumdichloride;-   Dimethylsilanediylbis[2-bicyclo[2.2.1]heptylmethyl-4-(1-naphthyl)-indenyl]zirconiumdichloride;-   Dimethylsilanediylbis[2-bicyclo[2.2.1]heptylmethyl-4-(2-naphthyl)-indenyl]zirconiumdichloride;-   Dimethylsilanediylbis[2-bicyclo[2.2.1]heptylmethyl-4-(4-methyl-phenyl)-indenyl]zirconiumdichloride;-   Dimethylsilanediylbis[2-bicyclo[2.2.1]heptylmethyl-4-(4-biphenyl)-indenyl]zirconiumdichloride;-   Dimethylsilanediylbis[2-bicyclo[2.2.1]heptylmethyl-4-(4-ethyl-phenyl)-indenyl]zirconiumdichloride;-   Dimethylsilanediylbis[2-bicyclo[2.2.1]heptylmethyl-4-(4-n-propyl-phenyl)-indenyl]zirconiumdichloride;-   Dimethylsilanediylbis[2-bicyclo[2.2.1]heptylmethyl-4-(4-i-propyl-phenyl)-indenyl]zirconiumdichloride;-   Dimethylsilanediylbis[2-bicyclo[2.2.1]heptylmethyl-4-(4-t-butyl-phenyl)-indenyl]zirconiumdichloride;-   Dimethylsilanediylbis[2-bicyclo[2.2.1]heptylmethyl-4-(4-sec-butyl-phenyl)-indenyl]zirconiumdichloride;-   Dimethylsilanediylbis[2-bicyclo[2.2.1]heptylmethyl-4-(4-cyclohexyl-phenyl)-indenyl]zirconiumdichloride;-   Dimethylsilanediylbis[2-bicyclo[2.2.1]heptylmethyl-4-(4-trimethylsilyl-phenyl)-indenyl]zirconiumdichloride;-   Dimethylsilanediylbis[2-bicyclo[2.2.1]heptylmethyl-4-(4-adamantyl-phenyl)-indenyl]zirconiumdichloride;-   Dimethylsilanediylbis[2-bicyclo[2.2.1]heptylmethyl-4-(3-biphenyl)-indenyl]zirconiumdichloride;-   Dimethylsilanediylbis[2-bicyclo[2.2.1]heptylmethyl-4-(3,5-dimethyl-phenyl)-indenyl]zirconiumdichloride;-   Dimethylsilanediylbis[2-bicyclo[2.2.1]heptylmethyl-4-(3,5-di-(trifluoromethyl)-phenyl)-indenyl]zirconiumdichloride;-   Dimethylsilanediylbis[2-bicyclo[2.2.1]heptylmethyl-4-(3,5-terphenyl)-indenyl]zirconiumdichloride;-   (Methyl)(n-propyl)silanediylbis[2-t-butylmethyl-4-(1-naphthyl)-indenyl]zirconiumdichloride;-   (Methyl)(n-propyl)silanediylbis[2-t-butylmethyl-4-(2-naphthyl)-indenyl]zirconiumdichloride;-   (Methyl)(n-propyl)silanediylbis[2-t-butylmethyl-4-(4-methyl-phenyl)-indenyl]zirconiumdichloride;-   (Methyl)(n-propyl)silanediylbis[2-t-butylmethyl-4-(4-biphenyl)-indenyl]zirconiumdichloride;-   (Methyl)(n-propyl)silanediylbis[2-t-butylmethyl-4-(4-ethyl-phenyl)-indenyl]zirconiumdichloride;-   (Methyl)(n-propyl)silanediylbis[2-t-butylmethyl-4-(4-n-propyl-phenyl)-indenyl]zirconiumdichloride;-   (Methyl)(n-propyl)silanediylbis[2-t-butylmethyl-4-(4-i-propyl-phenyl)-indenyl]zirconiumdichloride;-   (Methyl)(n-propyl)silanediylbis[2-t-butylmethyl-4-(4-t-butyl-phenyl)-indenyl]zirconiumdichloride;-   (Methyl)(n-propyl)silanediylbis[2-t-butylmethyl-4-(4-sec-butyl-phenyl)-indenyl]zirconiumdichloride;-   (Methyl)(n-propyl)silanediylbis[2-t-butylmethyl-4-(4-cyclohexyl-phenyl)-indenyl]zirconiumdichloride;-   (Methyl)(n-propyl)silanediylbis[2-t-butylmethyl-4-(4-trimethylsilyl-phenyl)-indenyl]zirconiumdichloride;-   (Methyl)(n-propyl)silanediylbis[2-t-butylmethyl-4-(4-adamantyl-phenyl)-indenyl]zirconiumdichloride;-   (Methyl)(n-propyl)silanediylbis[2-t-butylmethyl-4-(3-biphenyl)-indenyl]zirconiumdichloride;-   (Methyl)(n-propyl)silanediylbis[2-t-butylmethyl-4-(3,5-dimethyl-phenyl)-indenyl]zirconiumdichloride;-   (Methyl)(n-propyl)silanediylbis[2-t-butylmethyl-4-(3,5-di-(trifluoromethyl)-phenyl)-indenyl]zirconiumdichloride;-   (Methyl)(n-propyl)silanediylbis[2-t-butylmethyl-4-(3,5-terphenyl)-indenyl]zirconiumdichloride;-   (Methyl)(n-propyl)silanediylbis[2-cyclopentylmethyl-4-(1-naphthyl)-indenyl]zirconiumdichloride;-   (Methyl)(n-propyl)silanediylbis[2-cyclopentylmethyl-4-(2-naphthyl)-indenyl]zirconiumdichloride;-   (Methyl)(n-propyl)silanediylbis[2-cyclopentylmethyl-4-(4-methyl-phenyl)-indenyl]zirconiumdichloride;-   (Methyl)(n-propyl)silanediylbis[2-cyclopentylmethyl-4-(4-biphenyl)-indenyl]zirconiumdichloride;-   (Methyl)(n-propyl)silanediylbis[2-cyclopentylmethyl-4-(4-ethyl-phenyl)-indenyl]zirconiumdichloride;-   (Methyl)(n-propyl)silanediylbis[2-cyclopentylmethyl-4-(4-n-propyl-phenyl)-indenyl]zirconiumdichloride;-   (Methyl)(n-propyl)silanediylbis[2-cyclopentylmethyl-4-(4-i-propyl-phenyl)-indenyl]zirconiumdichloride;-   (Methyl)(n-propyl)silanediylbis[2-cyclopentylmethyl-4-(4-t-butyl-phenyl)-indenyl]zirconiumdichloride;-   (Methyl)(n-propyl)silanediylbis[2-cyclopentylmethyl-4-(4-sec-butyl-phenyl)-indenyl]zirconiumdichloride;-   (Methyl)(n-propyl)silanediylbis[2-cyclopentylmethyl-4-(4-cyclohexyl-phenyl)-indenyl]zirconiumdichloride;-   (Methyl)(n-propyl)silanediylbis[2-cyclopentylmethyl-4-(4-trimethylsilyl-phenyl)-indenyl]zirconiumdichloride;-   (Methyl)(n-propyl)silanediylbis[2-cyclopentylmethyl-4-(4-adamantyl-phenyl)-indenyl]zirconiumdichloride;-   (Methyl)(n-propyl)silanediylbis[2-cyclopentylmethyl-4-(3-biphenyl)-indenyl]zirconiumdichloride;-   (Methyl)(n-propyl)silanediylbis[2-cyclopentylmethyl-4-(3,5-dimethyl-phenyl)-indenyl]zirconiumdichloride;-   (Methyl)(n-propyl)silanediylbis[2-cyclopentylmethyl-4-(3,5-di-(trifluoromethyl)-phenyl)-indenyl]zirconiumdichloride;-   (Methyl)(n-propyl)silanediylbis[2-cyclopentylmethyl-4-(3,5-terphenyl)-indenyl]zirconiumdichloride;-   (Methyl)(n-propyl)silanediylbis[2-cyclohexylmethyl-4-(1-naphthyl)-indenyl]zirconiumdichloride;-   (Methyl)(n-propyl)silanediylbis[2-cyclohexylmethyl-4-(2-naphthyl)-indenyl]zirconiumdichloride;-   (Methyl)(n-propyl)silanediylbis[2-cyclohexylmethyl-4-(4-methyl-phenyl)-indenyl]zirconiumdichloride;-   (Methyl)(n-propyl)silanediylbis[2-cyclohexylmethyl-4-(4-biphenyl)-indenyl]zirconiumdichloride;-   (Methyl)(n-propyl)silanediylbis[2-cyclohexylmethyl-4-(4-ethyl-phenyl)-indenyl]zirconiumdichloride;-   (Methyl)(n-propyl)silanediylbis[2-cyclohexylmethyl-4-(4-n-propyl-phenyl)-indenyl]zirconiumdichloride;-   (Methyl)(n-propyl)silanediylbis[2-cyclohexylmethyl-4-(4-i-propyl-phenyl)-indenyl]zirconiumdichloride;-   (Methyl)(n-propyl)silanediylbis[2-cyclohexylmethyl-4-(4-t-butyl-phenyl)-indenyl]zirconiumdichloride;-   (Methyl)(n-propyl)silanediylbis[2-cyclohexylmethyl-4-(4-sec-butyl-phenyl)-indenyl]zirconiumdichloride;-   (Methyl)(n-propyl)silanediylbis[2-cyclohexylmethyl-4-(4-cyclohexyl-phenyl)-indenyl]zirconiumdichloride;-   (Methyl)(n-propyl)silanediylbis[2-cyclohexylmethyl-4-(4-trimethylsilyl-phenyl)-indenyl]zirconiumdichloride;-   (Methyl)(n-propyl)silanediylbis[2-cyclohexylmethyl-4-(4-adamantyl-phenyl)-indenyl]zirconiumdichloride;-   (Methyl)(n-propyl)silanediylbis[2-cyclohexylmethyl-4-(3-biphenyl)-indenyl]zirconiumdichloride;-   (Methyl)(n-propyl)silanediylbis[2-cyclohexylmethyl-4-(3,5-dimethyl-phenyl)-indenyl]zirconiumdichloride;-   (Methyl)(n-propyl)silanediylbis[2-cyclohexylmethyl-4-(3,5-di-(trifluoromethyl)-phenyl)-indenyl]zirconiumdichloride;-   (Methyl)(n-propyl)silanediylbis[2-cyclohexylmethyl-4-(3,5-terphenyl)-indenyl]zirconiumdichloride;-   (Methyl)(n-propyl)silanediylbis[2-cycloheptylmethyl-4-(1-naphthyl)-indenyl]zirconiumdichloride;-   (Methyl)(n-propyl)silanediylbis[2-cycloheptylmethyl-4-(2-naphthyl)-indenyl]zirconiumdichloride;-   (Methyl)(n-propyl)silanediylbis[2-cycloheptylmethyl-4-(4-methyl-phenyl)-indenyl]zirconiumdichloride;-   (Methyl)(n-propyl)silanediylbis[2-cycloheptylmethyl-4-(4-biphenyl)-indenyl]zirconiumdichloride;-   (Methyl)(n-propyl)silanediylbis[2-cycloheptylmethyl-4-(4-ethyl-phenyl)-indenyl]zirconiumdichloride;-   (Methyl)(n-propyl)silanediylbis[2-cycloheptylmethyl-4-(4-n-propyl-phenyl)-indenyl]zirconiumdichloride;-   (Methyl)(n-propyl)silanediylbis[2-cycloheptylmethyl-4-(4-i-propyl-phenyl)-indenyl]zirconiumdichloride;-   (Methyl)(n-propyl)silanediylbis[2-cycloheptylmethyl-4-(4-t-butyl-phenyl)-indenyl]zirconiumdichloride;-   (Methyl)(n-propyl)silanediylbis[2-cycloheptylmethyl-4-(4-sec-butyl-phenyl)-indenyl]zirconiumdichloride;-   (Methyl)(n-propyl)silanediylbis[2-cycloheptylmethyl-4-(4-cyclohexyl-phenyl)-indenyl]zirconiumdichloride;-   (Methyl)(n-propyl)silanediylbis[2-cycloheptylmethyl-4-(4-trimethylsilyl-phenyl)-indenyl]zirconiumdichloride;-   (Methyl)(n-propyl)silanediylbis[2-cycloheptylmethyl-4-(4-adamantyl-phenyl)-indenyl]zirconiumdichloride;-   (Methyl)(n-propyl)silanediylbis[2-cycloheptylmethyl-4-(3-biphenyl)-indenyl]zirconiumdichloride;-   (Methyl)(n-propyl)silanediylbis[2-cycloheptylmethyl-4-(3,5-dimethyl-phenyl)-indenyl]zirconiumdichloride;-   (Methyl)(n-propyl)silanediylbis[2-cycloheptylmethyl-4-(3,5-di-(trifluoromethyl)-phenyl)-indenyl]zirconiumdichloride;-   (Methyl)(n-propyl)silanediylbis[2-cycloheptylmethyl-4-(3,5-terphenyl)-indenyl]zirconiumdichloride;-   (Methyl)(n-propyl)silanediylbis[2-adamantylmethyl-4-(1-naphthyl)-indenyl]zirconiumdichloride;-   (Methyl)(n-propyl)silanediylbis[2-adamantylmethyl-4-(2-naphthyl)-indenyl]zirconiumdichloride;-   (Methyl)(n-propyl)silanediylbis[2-adamantylmethyl-4-(4-methyl-phenyl)-indenyl]zirconiumdichloride;-   (Methyl)(n-propyl)silanediylbis[2-adamantylmethyl-4-(4-biphenyl)-indenyl]zirconiumdichloride;-   (Methyl)(n-propyl)silanediylbis[2-adamantylmethyl-4-(4-ethyl-phenyl)-indenyl]zirconiumdichloride;-   (Methyl)(n-propyl)silanediylbis[2-adamantylmethyl-4-(4-n-propyl-phenyl)-indenyl]zirconiumdichloride;-   (Methyl)(n-propyl)silanediylbis[2-adamantylmethyl-4-(4-i-propyl-phenyl)-indenyl]zirconiumdichloride;-   (Methyl)(n-propyl)silanediylbis[2-adamantylmethyl-4-(4-t-butyl-phenyl)-indenyl]zirconiumdichloride;-   (Methyl)(n-propyl)silanediylbis[2-adamantylmethyl-4-(4-sec-butyl-phenyl)-indenyl]zirconiumdichloride;-   (Methyl)(n-propyl)silanediylbis[2-adamantylmethyl-4-(4-cyclohexyl-phenyl)-indenyl]zirconiumdichloride;-   (Methyl)(n-propyl)silanediylbis[2-adamantylmethyl-4-(4-trimethylsilyl-phenyl)-indenyl]zirconiumdichloride;-   (Methyl)(n-propyl)silanediylbis[2-adamantylmethyl-4-(4-adamantyl-phenyl)-indenyl]zirconiumdichloride;-   (Methyl)(n-propyl)silanediylbis[2-adamantylmethyl-4-(3-biphenyl)-indenyl]zirconiumdichloride;-   (Methyl)(n-propyl)silanediylbis[2-adamantylmethyl-4-(3,5-dimethyl-phenyl)-indenyl]zirconiumdichloride;-   (Methyl)(n-propyl)silanediylbis[2-adamantylmethyl-4-(3,5-di-(trifluoromethyl)-phenyl)-indenyl]zirconiumdichloride;-   (Methyl)(n-propyl)silanediylbis[2-adamantylmethyl-4-(3,5-terphenyl)-indenyl]zirconiumdichloride;-   (Methyl)(n-propyl)silanediylbis[2-bicyclo[2.2.1]heptylmethyl-4-(1-naphthyl)-indenyl]zirconiumdichloride;-   (Methyl)(n-propyl)silanediylbis[2-bicyclo[2.2.1]heptylmethyl-4-(2-naphthyl)-indenyl]zirconiumdichloride;-   (Methyl)(n-propyl)silanediylbis[2-bicyclo[2.2.1]heptylmethyl-4-(4-methyl-phenyl)-indenyl]zirconiumdichloride;-   (Methyl)(n-propyl)silanediylbis[2-bicyclo[2.2.1]heptylmethyl-4-(4-biphenyl)-indenyl]zirconiumdichloride;-   (Methyl)(n-propyl)silanediylbis[2-bicyclo[2.2.1]heptylmethyl-4-(4-ethyl-phenyl)-indenyl]zirconiumdichloride;-   (Methyl)(n-propyl)silanediylbis[2-bicyclo[2.2.1]heptylmethyl-4-(4-n-propyl-phenyl)-indenyl]zirconiumdichloride;-   (Methyl)(n-propyl)silanediylbis[2-bicyclo[2.2.1]heptylmethyl-4-(4-i-propyl-phenyl)-indenyl]zirconiumdichloride;-   (Methyl)(n-propyl)silanediylbis[2-bicyclo[2.2.1]heptylmethyl-4-(4-t-butyl-phenyl)-indenyl]zirconiumdichloride;-   (Methyl)(n-propyl)silanediylbis[2-bicyclo[2.2.1]heptylmethyl-4-(4-sec-butyl-phenyl)-indenyl]zirconiumdichloride;-   (Methyl)(n-propyl)silanediylbis[2-bicyclo[2.2.1]heptylmethyl-4-(4-cyclohexyl-phenyl)-indenyl]zirconiumdichloride;-   (Methyl)(n-propyl)silanediylbis[2-bicyclo[2.2.1]heptylmethyl-4-(4-trimethylsilyl-phenyl)-indenyl]zirconiumdichloride;-   (Methyl)(n-propyl)silanediylbis[2-bicyclo[2.2.1]heptylmethyl-4-(4-adamantyl-phenyl)-indenyl]zirconiumdichloride;-   (Methyl)(n-propyl)silanediylbis[2-bicyclo[2.2.1]heptylmethyl-4-(3-biphenyl)-indenyl]zirconiumdichloride;-   (Methyl)(n-propyl)silanediylbis[2-bicyclo[2.2.1]heptylmethyl-4-(3,5-dimethyl-phenyl)-indenyl]zirconiumdichloride;-   (Methyl)(n-propyl)silanediylbis[2-bicyclo[2.2.1]heptylmethyl-4-(3,5-di-(trifluoromethyl)-phenyl)-indenyl]zirconiumdichloride;-   (Methyl)(n-propyl)silanediylbis[2-bicyclo[2.2.1]heptylmethyl-4-(3,5-terphenyl)-indenyl]zirconiumdichloride;-   (Methyl)(3,3,3-trifluoropropyl)silanediylbis[2-t-butylmethyl-4-(1-naphthyl)-indenyl]zirconiumdichloride;-   (Methyl)(3,3,3-trifluoropropyl)silanediylbis[2-t-butylmethyl-4-(2-naphthyl)-indenyl]zirconiumdichloride;-   (Methyl)(3,3,3-trifluoropropyl)silanediylbis[2-t-butylmethyl-4-(4-methyl-phenyl)-indenyl]zirconiumdichloride;-   (Methyl)(3,3,3-trifluoropropyl)silanediylbis[2-t-butylmethyl-4-(4-biphenyl)-indenyl]zirconiumdichloride;-   (Methyl)(3,3,3-trifluoropropyl)silanediylbis[2-t-butylmethyl-4-(4-ethyl-phenyl)-indenyl]zirconiumdichloride;-   (Methyl)(3,3,3-trifluoropropyl)silanediylbis[2-t-butylmethyl-4-(4-n-propyl-phenyl)-indenyl]zirconiumdichloride;-   (Methyl)(3,3,3-trifluoropropyl)silanediylbis[2-t-butylmethyl-4-(4-i-propyl-phenyl)-indenyl]zirconiumdichloride;-   (Methyl)(3,3,3-trifluoropropyl)silanediylbis[2-t-butylmethyl-4-(4-t-butyl-phenyl)-indenyl]zirconiumdichloride;-   (Methyl)(3,3,3-trifluoropropyl)silanediylbis[2-t-butylmethyl-4-(4-sec-butyl-phenyl)-indenyl]zirconiumdichloride;-   (Methyl)(3,3,3-trifluoropropyl)silanediylbis[2-t-butylmethyl-4-(4-cyclohexyl-phenyl)-indenyl]zirconiumdichloride;-   (Methyl)(3,3,3-trifluoropropyl)silanediylbis[2-t-butylmethyl-4-(4-trimethylsilyl-phenyl)-indenyl]zirconiumdichloride;-   (Methyl)(3,3,3-trifluoropropyl)silanediylbis[2-t-butylmethyl-4-(4-adamantyl-phenyl)-indenyl]zirconiumdichloride;-   (Methyl)(3,3,3-trifluoropropyl)silanediylbis[2-t-butylmethyl-4-(3-biphenyl)-indenyl]zirconiumdichloride;-   (Methyl)(3,3,3-trifluoropropyl)silanediylbis[2-t-butylmethyl-4-(3,5-dimethyl-phenyl)-indenyl]zirconiumdichloride;-   (Methyl)(3,3,3-trifluoropropyl)silanediylbis[2-t-butylmethyl-4-(3,5-di-(trifluoromethyl)-phenyl)-indenyl]zirconiumdichloride;-   (Methyl)(3,3,3-trifluoropropyl)silanediylbis[2-t-butylmethyl-4-(3,5-terphenyl)-indenyl]zirconiumdichloride;-   (Methyl)(3,3,3-trifluoropropyl)silanediylbis[2-cyclopentylmethyl-4-(1-naphthyl)-indenyl]zirconiumdichloride;-   (Methyl)(3,3,3-trifluoropropyl)silanediylbis[2-cyclopentylmethyl-4-(2-naphthyl)-indenyl]zirconiumdichloride;-   (Methyl)(3,3,3-trifluoropropyl)silanediylbis[2-cyclopentylmethyl-4-(4-methyl-phenyl)-indenyl]zirconiumdichloride;-   (Methyl)(3,3,3-trifluoropropyl)silanediylbis[2-cyclopentylmethyl-4-(4-biphenyl)-indenyl]zirconiumdichloride;-   (Methyl)(3,3,3-trifluoropropyl)silanediylbis[2-cyclopentylmethyl-4-(4-ethyl-phenyl)-indenyl]zirconiumdichloride;-   (Methyl)(3,3,3-trifluoropropyl)silanediylbis[2-cyclopentylmethyl-4-(4-n-propyl-phenyl)-indenyl]zirconiumdichloride;-   (Methyl)(3,3,3-trifluoropropyl)silanediylbis[2-cyclopentylmethyl-4-(4-i-propyl-phenyl)-indenyl]zirconiumdichloride;-   (Methyl)(3,3,3-trifluoropropyl)silanediylbis[2-cyclopentylmethyl-4-(4-t-butyl-phenyl)-indenyl]zirconiumdichloride;-   (Methyl)(3,3,3-trifluoropropyl)silanediylbis[2-cyclopentylmethyl-4-(4-sec-butyl-phenyl)-indenyl]zirconiumdichloride;-   (Methyl)(3,3,3-trifluoropropyl)silanediylbis[2-cyclopentylmethyl-4-(4-cyclohexyl-phenyl)-indenyl]zirconiumdichloride;-   (Methyl)(3,3,3-trifluoropropyl)silanediylbis[2-cyclopentylmethyl-4-(4-trimethylsilyl-phenyl)-indenyl]zirconiumdichloride;-   (Methyl)(3,3,3-trifluoropropyl)silanediylbis[2-cyclopentylmethyl-4-(4-adamantyl-phenyl)-indenyl]zirconiumdichloride;-   (Methyl)(3,3,3-trifluoropropyl)silanediylbis[2-cyclopentylmethyl-4-(3-biphenyl)-indenyl]zirconiumdichloride;-   (Methyl)(3,3,3-trifluoropropyl)silanediylbis[2-cyclopentylmethyl-4-(3,5-dimethyl-phenyl)-indenyl]zirconiumdichloride;-   (Methyl)(3,3,3-trifluoropropyl)silanediylbis[2-cyclopentylmethyl-4-(3,5-di-(trifluoromethyl)-phenyl)-indenyl]zirconiumdichloride;-   (Methyl)(3,3,3-trifluoropropyl)silanediylbis[2-cyclopentylmethyl-4-(3,5-terphenyl)-indenyl]zirconiumdichloride;-   (Methyl)(3,3,3-trifluoropropyl)silanediylbis[2-cyclohexylmethyl-4-(1-naphthyl)-indenyl]zirconiumdichloride;-   (Methyl)(3,3,3-trifluoropropyl)silanediylbis[2-cyclohexylmethyl-4-(2-naphthyl)-indenyl]zirconiumdichloride;-   (Methyl)(3,3,3-trifluoropropyl)silanediylbis[2-cyclohexylmethyl-4-(4-methyl-phenyl)-indenyl]zirconiumdichloride;-   (Methyl)(3,3,3-trifluoropropyl)silanediylbis[2-cyclohexylmethyl-4-(4-biphenyl)-indenyl]zirconiumdichloride;-   (Methyl)(3,3,3-trifluoropropyl)silanediylbis[2-cyclohexylmethyl-4-(4-ethyl-phenyl)-indenyl]zirconiumdichloride;-   (Methyl)(3,3,3-trifluoropropyl)silanediylbis[2-cyclohexylmethyl-4-(4-n-propyl-phenyl)-indenyl]zirconiumdichloride;-   (Methyl)(3,3,3-trifluoropropyl)silanediylbis[2-cyclohexylmethyl-4-(4-i-propyl-phenyl)-indenyl]zirconiumdichloride;-   (Methyl)(3,3,3-trifluoropropyl)silanediylbis[2-cyclohexylmethyl-4-(4-t-butyl-phenyl)-indenyl]zirconiumdichloride;-   (Methyl)(3,3,3-trifluoropropyl)silanediylbis[2-cyclohexylmethyl-4-(4-sec-butyl-phenyl)-indenyl]zirconiumdichloride;-   (Methyl)(3,3,3-trifluoropropyl)silanediylbis[2-cyclohexylmethyl-4-(4-cyclohexyl-phenyl)-indenyl]zirconiumdichloride;-   (Methyl)(3,3,3-trifluoropropyl)silanediylbis[2-cyclohexylmethyl-4-(4-trimethylsilyl-phenyl)-indenyl]zirconiumdichloride;-   (Methyl)(3,3,3-trifluoropropyl)silanediylbis[2-cyclohexylmethyl-4-(4-adamantyl-phenyl)-indenyl]zirconiumdichloride;-   (Methyl)(3,3,3-trifluoropropyl)silanediylbis[2-cyclohexylmethyl-4-(3-biphenyl)-indenyl]zirconiumdichloride;-   (Methyl)(3,3,3-trifluoropropyl)silanediylbis[2-cyclohexylmethyl-4-(3,5-dimethyl-phenyl)-indenyl]zirconiumdichloride;-   (Methyl)(3,3,3-trifluoropropyl)silanediylbis[2-cyclohexylmethyl-4-(3,5-di-(trifluoromethyl)-phenyl)-indenyl]zirconiumdichloride;-   (Methyl)(3,3,3-trifluoropropyl)silanediylbis[2-cyclohexylmethyl-4-(3,5-terphenyl)-indenyl]zirconiumdichloride;-   (Methyl)(3,3,3-trifluoropropyl)silanediylbis[2-cycloheptylmethyl-4-(1-naphthyl)-indenyl]zirconiumdichloride;-   (Methyl)(3,3,3-trifluoropropyl)silanediylbis[2-cycloheptylmethyl-4-(2-naphthyl)-indenyl]zirconiumdichloride;-   (Methyl)(3,3,3-trifluoropropyl)silanediylbis[2-cycloheptylmethyl-4-(4-methyl-phenyl)-indenyl]zirconiumdichloride;-   (Methyl)(3,3,3-trifluoropropyl)silanediylbis[2-cycloheptylmethyl-4-(4-biphenyl)-indenyl]zirconiumdichloride;-   (Methyl)(3,3,3-trifluoropropyl)silanediylbis[2-cycloheptylmethyl-4-(4-ethyl-phenyl)-indenyl]zirconiumdichloride;-   (Methyl)(3,3,3-trifluoropropyl)silanediylbis[2-cycloheptylmethyl-4-(4-n-propyl-phenyl)-indenyl]zirconiumdichloride;-   (Methyl)(3,3,3-trifluoropropyl)silanediylbis[2-cycloheptylmethyl-4-(4-i-propyl-phenyl)-indenyl]zirconiumdichloride;-   (Methyl)(3,3,3-trifluoropropyl)silanediylbis[2-cycloheptylmethyl-4-(4-t-butyl-phenyl)-indenyl]zirconiumdichloride;-   (Methyl)(3,3,3-trifluoropropyl)silanediylbis[2-cycloheptylmethyl-4-(4-sec-butyl-phenyl)-indenyl]zirconiumdichloride;-   (Methyl)(3,3,3-trifluoropropyl)silanediylbis[2-cycloheptylmethyl-4-(4-cyclohexyl-phenyl)-indenyl]zirconiumdichloride;-   (Methyl)(3,3,3-trifluoropropyl)silanediylbis[2-cycloheptylmethyl-4-(4-trimethylsilyl-phenyl)-indenyl]zirconiumdichloride;-   (Methyl)(3,3,3-trifluoropropyl)silanediylbis[2-cycloheptylmethyl-4-(4-adamantyl-phenyl)-indenyl]zirconiumdichloride;-   (Methyl)(3,3,3-trifluoropropyl)silanediylbis[2-cycloheptylmethyl-4-(3-biphenyl)-indenyl]zirconiumdichloride;-   (Methyl)(3,3,3-trifluoropropyl)silanediylbis[2-cycloheptylmethyl-4-(3,5-dimethyl-phenyl)-indenyl]zirconiumdichloride;-   (Methyl)(3,3,3-trifluoropropyl)silanediylbis[2-cycloheptylmethyl-4-(3,5-di-(trifluoromethyl)-phenyl)-indenyl]zirconiumdichloride;-   (Methyl)(3,3,3-trifluoropropyl)silanediylbis[2-cycloheptylmethyl-4-(3,5-terphenyl)-indenyl]zirconiumdichloride;-   (Methyl)(3,3,3-trifluoropropyl)silanediylbis[2-adamantylmethyl-4-(1-naphthyl)-indenyl]zirconiumdichloride;-   (Methyl)(3,3,3-trifluoropropyl)silanediylbis[2-adamantylmethyl-4-(2-naphthyl)-indenyl]zirconiumdichloride;-   (Methyl)(3,3,3-trifluoropropyl)silanediylbis[2-adamantylmethyl-4-(4-methyl-phenyl)-indenyl]zirconiumdichloride;-   (Methyl)(3,3,3-trifluoropropyl)silanediylbis[2-adamantylmethyl-4-(4-biphenyl)-indenyl]zirconiumdichloride;-   (Methyl)(3,3,3-trifluoropropyl)silanediylbis[2-adamantylmethyl-4-(4-ethyl-phenyl)-indenyl]zirconiumdichloride;-   (Methyl)(3,3,3-trifluoropropyl)silanediylbis[2-adamantylmethyl-4-(4-n-propyl-phenyl)-indenyl]zirconiumdichloride;-   (Methyl)(3,3,3-trifluoropropyl)silanediylbis[2-adamantylmethyl-4-(4-i-propyl-phenyl)-indenyl]zirconiumdichloride;-   (Methyl)(3,3,3-trifluoropropyl)silanediylbis[2-adamantylmethyl-4-(4-t-butyl-phenyl)-indenyl]zirconiumdichloride;-   (Methyl)(3,3,3-trifluoropropyl)silanediylbis[2-adamantylmethyl-4-(4-sec-butyl-phenyl)-indenyl]zirconiumdichloride;-   (Methyl)(3,3,3-trifluoropropyl)silanediylbis[2-adamantylmethyl-4-(4-cyclohexyl-phenyl)-indenyl]zirconiumdichloride;-   (Methyl)(3,3,3-trifluoropropyl)silanediylbis[2-adamantylmethyl-4-(4-trimethylsilyl-phenyl)-indenyl]zirconiumdichloride;-   (Methyl)(3,3,3-trifluoropropyl)silanediylbis[2-adamantylmethyl-4-(4-adamantyl-phenyl)-indenyl]zirconiumdichloride;-   (Methyl)(3,3,3-trifluoropropyl)silanediylbis[2-adamantylmethyl-4-(3-biphenyl)-indenyl]zirconiumdichloride;-   (Methyl)(3,3,3-trifluoropropyl)silanediylbis[2-adamantylmethyl-4-(3,5-dimethyl-phenyl)-indenyl]zirconiumdichloride;-   (Methyl)(3,3,3-trifluoropropyl)silanediylbis[2-adamantylmethyl-4-(3,5-di-(trifluoromethyl)-phenyl)-indenyl]zirconiumdichloride;-   (Methyl)(3,3,3-trifluoropropyl)silanediylbis[2-adamantylmethyl-4-(3,5-terphenyl)-indenyl]zirconiumdichloride;-   (Methyl)(3,3,3-trifluoropropyl)silanediylbis[2-bicyclo[2.2.1]heptylmethyl-4-(1-naphthyl)-indenyl]zirconiumdichloride;-   (Methyl)(3,3,3-trifluoropropyl)silanediylbis[2-bicyclo[2.2.1]heptylmethyl-4-(2-naphthyl)-indenyl]zirconiumdichloride;-   (Methyl)(3,3,3-trifluoropropyl)silanediylbis[2-bicyclo[2.2.1]heptylmethyl-4-(4-methyl-phenyl)-indenyl]zirconiumdichloride;-   (Methyl)(3,3,3-trifluoropropyl)silanediylbis[2-bicyclo[2.2.1]heptylmethyl-4-(4-biphenyl)-indenyl]zirconiumdichloride;-   (Methyl)(3,3,3-trifluoropropyl)silanediylbis[2-bicyclo[2.2.1]heptylmethyl-4-(4-ethyl-phenyl)-indenyl]zirconiumdichloride;-   (Methyl)(3,3,3-trifluoropropyl)silanediylbis[2-bicyclo[2.2.1]heptylmethyl-4-(4-n-propyl-phenyl)-indenyl]zirconiumdichloride;-   (Methyl)(3,3,3-trifluoropropyl)silanediylbis[2-bicyclo[2.2.1]heptylmethyl-4-(4-i-propyl-phenyl)-indenyl]zirconiumdichloride;-   (Methyl)(3,3,3-trifluoropropyl)silanediylbis[2-bicyclo[2.2.1]heptylmethyl-4-(4-t-butyl-phenyl)-indenyl]zirconiumdichloride;-   (Methyl)(3,3,3-trifluoropropyl)silanediylbis[2-bicyclo[2.2.1]heptylmethyl-4-(4-sec-butyl-phenyl)-indenyl]zirconiumdichloride;-   (Methyl)(3,3,3-trifluoropropyl)silanediylbis[2-bicyclo[2.2.1]heptylmethyl-4-(4-cyclohexyl-phenyl)-indenyl]zirconiumdichloride;-   (Methyl)(3,3,3-trifluoropropyl)silanediylbis[2-bicyclo[2.2.1]heptylmethyl-4-(4-trimethylsilyl-phenyl)-indenyl]zirconiumdichloride;-   (Methyl)(3,3,3-trifluoropropyl)silanediylbis[2-bicyclo[2.2.1]heptylmethyl-4-(4-adamantyl-phenyl)-indenyl]zirconiumdichloride;-   (Methyl)(3,3,3-trifluoropropyl)silanediylbis[2-bicyclo[2.2.1]heptylmethyl-4-(3-biphenyl)-indenyl]zirconiumdichloride;-   (Methyl)(3,3,3-trifluoropropyl)silanediylbis[2-bicyclo[2.2.1]heptylmethyl-4-(3,5-dimethyl-phenyl)-indenyl]zirconiumdichloride;-   (Methyl)(3,3,3-trifluoropropyl)silanediylbis[2-bicyclo[2.2.1]heptylmethyl-4-(3,5-di-(trifluoromethyl)-phenyl)-indenyl]zirconiumdichloride;-   (Methyl)(3,3,3-trifluoropropyl)silanediylbis[2-bicyclo[2.2.1]heptylmethyl-4-(3,5-terphenyl)-indenyl]zirconiumdichloride;-   Dimethylsilanediylbis[2-cyclohexylmethyl-4-(1-naphthyl)-6-methylindenyl]zirconiumdichloride;-   Dimethylsilanediylbis[2-cyclohexylmethyl-4-(2-naphthyl)-6-methylindenyl]zirconiumdichloride;-   Dimethylsilanediylbis[2-cyclohexylmethyl-4-(4-methyl-phenyl)-6-methylindenyl]zirconiumdichloride;-   Dimethylsilanediylbis[2-cyclohexylmethyl-4-(4-biphenyl)-6-methylindenyl]zirconiumdichloride;-   Dimethylsilanediylbis[2-cyclohexylmethyl-4-(4-ethyl-phenyl)-6-methylindenyl]zirconiumdichloride;-   Dimethylsilanediylbis[2-cyclohexylmethyl-4-(4-n-propyl-phenyl)-6-methylindenyl]zirconiumdichloride;-   Dimethylsilanediylbis[2-cyclohexylmethyl-4-(4-i-propyl-phenyl)-6-methylindenyl]zirconiumdichloride;-   Dimethylsilanediylbis[2-cyclohexylmethyl-4-(4-t-butyl-phenyl)-6-methylindenyl]zirconiumdichloride;-   Dimethylsilanediylbis[2-cyclohexylmethyl-4-(4-sec-butyl-phenyl)-6-methylindenyl]zirconiumdichloride;-   Dimethylsilanediylbis[2-cyclohexylmethyl-4-(4-cyclohexyl-phenyl)-6-methylindenyl]zirconiumdichloride;-   Dimethylsilanediylbis[2-cyclohexylmethyl-4-(4-trimethylsilyl-phenyl)-6-methylindenyl]zirconiumdichloride;-   Dimethylsilanediylbis[2-cyclohexylmethyl-4-(4-adamantyl-phenyl)-6-methylindenyl]zirconiumdichloride;-   Dimethylsilanediylbis[2-cyclohexylmethyl-4-(3-biphenyl)-6-methylindenyl]zirconiumdichloride;-   Dimethylsilanediylbis[2-cyclohexylmethyl-4-(3,5-dimethyl-phenyl)-6-methylindenyl]zirconiumdichloride;-   Dimethylsilanediylbis[2-cyclohexylmethyl-4-(3,5-di-(trifluoromethyl)-phenyl)-6-methylindenyl]zirconiumdichloride;-   Dimethylsilanediylbis[2-cyclohexylmethyl-4-(3,5-terphenyl)-6-methylindenyl]zirconiumdichloride;-   Dimethylsilanediylbis[2-cyclohexylmethyl-4-(1-naphthyl)-7-methylindenyl]zirconiumdichloride;-   Dimethylsilanediylbis[2-cyclohexylmethyl-4-(2-naphthyl)-7-methylindenyl]zirconiumdichloride;-   Dimethylsilanediylbis[2-cyclohexylmethyl-4-(4-methyl-phenyl)-7-methylindenyl]zirconiumdichloride;-   Dimethylsilanediylbis[2-cyclohexylmethyl-4-(4-biphenyl)-7-methylindenyl]zirconiumdichloride;-   Dimethylsilanediylbis[2-cyclohexylmethyl-4-(4-ethyl-phenyl)-7-methylindenyl]zirconiumdichloride;-   Dimethylsilanediylbis[2-cyclohexylmethyl-4-(4-n-propyl-phenyl)-7-methylindenyl]zirconiumdichloride;-   Dimethylsilanediylbis[2-cyclohexylmethyl-4-(4-i-propyl-phenyl)-7-methylindenyl]zirconiumdichloride;-   Dimethylsilanediylbis[2-cyclohexylmethyl-4-(4-t-butyl-phenyl)-7-methylindenyl]zirconiumdichloride;-   Dimethylsilanediylbis[2-cyclohexylmethyl-4-(4-sec-butyl-phenyl)-7-methylindenyl]zirconiumdichloride;-   Dimethylsilanediylbis[2-cyclohexylmethyl-4-(4-cyclohexyl-phenyl)-7-methylindenyl]zirconiumdichloride;-   Dimethylsilanediylbis[2-cyclohexylmethyl-4-(4-trimethylsilyl-phenyl)-7-methylindenyl]zirconiumdichloride;-   Dimethylsilanediylbis[2-cyclohexylmethyl-4-(4-adamantyl-phenyl)-7-methylindenyl]zirconiumdichloride;-   Dimethylsilanediylbis[2-cyclohexylmethyl-4-(3-biphenyl)-7-methylindenyl]zirconiumdichloride;-   Dimethylsilanediylbis[2-cyclohexylmethyl-4-(3,5-dimethyl-phenyl)-7-methylindenyl]zirconiumdichloride;-   Dimethylsilanediylbis[2-cyclohexylmethyl-4-(3,5-di-(trifluoromethyl)-phenyl)-7-methylindenyl]zirconiumdichloride;-   Dimethylsilanediylbis[2-cyclohexylmethyl-4-(3,5-terphenyl)-7-methylindenyl]zirconiumdichloride,    as well as the analogous zirconiumdimethyl-compounds and    zirconium-biphenolates and zirconium-bisphenolates.

Instead of the preferred pure chiral bridged racemic or pseudoracemicmetallocene compounds of formulas 1 and 1a, mixtures of the metallocenesof formulas 1 and 1a and the corresponding meso or pseudomesometallocenes may be used in the catalyst preparation. However, thepreparation of the isomerically pure racemic form is especiallypreferred for the use of metallocenes in the polymerization of olefinsto isotactic polyolefins, since the corresponding meso form may produceundesired atactic polypropylene (“PP”). The “isomerically pure” racemicform is understood to mean a rac:meso ratio of greater than 5:1preferably of at least 10:1, more preferred of at least 15:1 and mostpreferred of at least 20:1.

As used herein the term “racemic” (or “rac”) includes “pseudoracemic”(or “pseudorac”), and the term “meso” includes “pseudomeso.”

The present invention also includes a process for producing thetransition-metal compounds of formulas 1 and 1a of the invention.

An object of the invention is thus a process for producing compounds offormula 1a,

in which the variables R and M¹ have the meaning specified above,including the preferred embodiments, comprising the steps of:

-   -   a) Deprotonation of the compound of formula 2:

-   -   with a base, in which R³⁰⁰, R^(4′), R^(5′), R^(6′), R^(7′), and        R^(8′) have the meaning specified above.    -   b) If R¹⁰ has the meaning M¹²R⁴⁰R⁴¹, where M¹², R⁴⁰, and R⁴¹        have the meanings specified above, then the further production        proceeds by the reaction of the deprotonated compounds from        step (a) with R⁴⁰R⁴¹M¹²X₂ to form the compound of formula 3 or        formula 4, depending on the quantitative proportions used, where        R⁴⁰, R⁴¹, and M¹² have the meanings specified above, and X may        be the same or different and means a halogen atom, preferably        chlorine, bromine, or iodine, or another leaving group,        preferably triflate, tosylate, or mesylate.

-   -   c) After the production of chlorosilane indenes or chlorogermane        indenes of formula 3, these are reacted with a metal-indene        compound of formula 5

-   -   -   in which M stands for Li, Na, or K, and R³, R⁴, R⁵, R⁶, R⁷,            K and R⁸ have the meanings specified above, to obtain the            compound of formula 6.

-   -   d) Reaction of the compound of formula 4 or 6 with a base and        addition of M¹Cl₄, in which M¹ stands for zirconium, titanium,        or hafnium, to form the compound of formula 1a.

In step (a), the compound of formula 2, for example,2-(cyclohexylmethyl)-7-(4′-tert-butylphenyl)indene in an inert solvent,which consists of one or more aromatic or aliphatic hydrocarbons and/orone or more polar, aprotic solvents, is deprotonated with a strong base,for example, n-butyllithium. The deprotonation is carried out attemperatures of −70° C. to 80° C., and preferably 0° C. to 80° C. Theresulting metal salt is then reacted directly, without furtherisolation, in step (b) with a silicon compound or germanium compoundthat contains two leaving groups. Preferential production of thecompound of formula 3 or the compound of formula 4 can be achieved byadjustment of the quantitative proportions. Compounds of formula 3 arereacted in step (c) with a metal-indenyl compound of formula 5. In thefollowing step (d), the bis(indenyl)silanes of formula 4 or 6 are doublydeprotonated with a strong base, such as n-butyllithium, in an inertsolvent, which consists of one or more aromatic or aliphatichydrocarbons and/or one or more polar, aprotic solvents, and thebislithium salt formed in this way is reacted, without isolation,directly with a source of Ti, Zr, or Hf to obtain the compound offormula 1a. The deprotonation is carried out at temperatures of −70° C.to 80° C., and preferably 0° C. to 80° C. Depending on the nature of theligand system of formula 4 or 6, the metallocenes are isolated directlyfrom the reaction mixture with rac:meso ratios or pseudo-rac:meso ratiosof greater than 5:1 preferably of at least 10:1, more preferred of atleast 15:1 and most preferred of at least 20:1 or further rac:mesoseparation steps have to be applied to reach rac:meso ratios orpseudo-rac:meso ratios of at least 5:1 preferably of at least 10:1, morepreferred of at least 15:1 and most preferred of at least 20:1 to obtaina suitable catalyst.

In FIG. 1, the individual steps of the process of the invention forproducing transition-metal compounds of formulas 1a are shown once againfor the example of a preferred embodiment.

In addition, the present invention relates to a catalyst systemcomprising at least one compound of formulas 1 or 1a and at least onecocatalyst.

A suitable cocatalyst component which may be present according to thepresent invention in the catalyst system comprises at least one compoundof the type of an aluminoxane, a Lewis acid or an ionic compound whichreacts with a metallocene to convert the latter into a cationiccompound.

Aluminoxanes are oligomeric or polymeric aluminum oxy compounds, whichmay exist in the form of linear, cyclic, caged or polymeric structures.Although the exact structure(s) of aluminoxanes is still unknown, it iswell accepted that alkylaluminoxanes have the general formula 7.

(R-AI—O)_(p)  (Formula 7).

Examples for cyclic, linear or cage structures of aluminoxanes aredepicted in the formulas 8, 9 and 10:

The radicals R in the formulas (7), (8), (9) and (10) can be identicalor different and are each a C₁-C₂₀ group such as an alkyl group of from1 to about 6 carbon atoms, an aryl group of from 6 to about 18 carbonatoms, benzyl or hydrogen and p is an integer from 2 to 50, preferablyfrom 10 to 35.

Preferably, the radicals R are identical and are methyl, isobutyl,n-butyl, phenyl or benzyl, particularly preferably methyl.

If the radicals R are different, they are preferably methyl andhydrogen, methyl and isobutyl or methyl and n-butyl, with hydrogen,isobutyl or n-butyl preferably being present in a proportion of from0.01 to 40% (number of radicals R).

The aluminoxane can be prepared in various ways by known methods. One ofthe methods comprises the reaction of an aluminum-hydrocarbon compoundand/or a hydridoaluminum-hydrocarbon compound with water, which may begaseous, solid, liquid or bound as water of crystallization, in an inertsolvent such as toluene. To prepare an aluminoxane having differentalkyl groups R, two different trialkylaluminums (AlR₃+AlR′₃)corresponding to the desired composition and reactivity are reacted withwater, cf. S. Pasynkiewicz, Polyhedron 9 (1990) 429 and EP-A-0 302 424.

Regardless of the method of preparation, all aluminoxane solutions havein common a variable content of unreacted aluminum starting compoundwhich is present in free form or as an adduct.

Furthermore, instead of the aluminoxane compounds of the formulas 7, 8,9 or 10, it is also possible to use modified aluminoxanes in which thehydrocarbon radicals or hydrogen atoms have been partly replaced byalkoxy, aryloxy, siloxy or amide radicals.

The amounts of aluminoxane and metallocene used in the preparation ofthe supported catalyst system can be varied within a wide range.However, it has been found to be advantageous to use the metallocenecompound of formulas 1 or 1a and the aluminoxane compounds in suchamounts that the atomic ratio of aluminum from the aluminoxane compoundsto the transition metal from the metallocene compound is in the rangefrom 10:1 to 1000:1, preferably from 20:1 to 500:1 and in particular inthe range from 30:1 to 400:1. In the case of methylaluminoxane,preference is given to using ≧30% strength toluene solutions, but theuse of 10% strength solutions is also possible.

As Lewis acid, preference is given to using compounds of the formula 11

M²X¹X²X³  (Formula 11)

where M² is an element of Group 13 of the Periodic Table of Elements, inparticular B, Al or Ga, preferably B or Al, X¹, X² and X³ are the sameor different and each are a hydrogen atom, an alkyl group of from 1 toabout 20 carbon atoms, an aryl group of from 6 to about 15 carbon atoms,alkylaryl, arylalkyl, haloalkyl or haloaryl each having from 1 to 10carbon atoms in the alkyl radical and from 6-20 carbon atoms in the arylradical or fluorine, chlorine, bromine or iodine. Preferred examples forX¹, X² and X³ are methyl, propyl, isopropyl, isobutyl ortrifluoromethyl, unsaturated groups such as aryl or haloaryl likephenyl, tolyl, benzyl groups, p-fluorophenyl, 3,5-difluorophenyl,pentachlorophenyl, pentafluorophenyl, 3,4,5-trifluorophenyl and3,5-di(trifluoromethyl)phenyl.

Preferred Lewis acids are trimethylaluminum, triethylaluminum,triisobutylaluminum, tributylaluminum, trifluoroborane, triphenylborane,tris(4-fluorophenyl)borane, tris(3,5-difluorophenyl)borane,tris(4-fluoromethylphenyl)borane, tris(2,4,6-trifluorophenyl)borane,tris(penta-fluorophenyl)borane, tris(tolyl)borane,tris(3,5-dimethyl-phenyl)borane, tris(3,5-difluorophenyl)borane and/ortris(3,4,5-trifluorophenyl)borane.

Particular preference is given to tris(pentafluorophenyl)borane.

As ionic cocatalysts, preference is given to using compounds whichcontain a non-coordinating anion such astetrakis(pentafluorophenyl)borate, tetraphenylborate, SbF₆ ⁻, CF₃SO₃ ⁻or ClO₄ ⁻. Suitable counterions are either Lewis acid or Broenstedt acidcation.

As Broensted acids, particular preference is given to protonated amineor aniline derivatives such as methylammonium, anilinium,dimethylammonium, diethylammonium, N-methylanilinium, diphenylammonium,N,N-dimethylanilinium, trimethylammonium, triethylammonium,tri-n-butylammonium, methyldiphenylammonium, pyridinium,p-bromo-N,N-dimethylanilinium or p-nitro-N,N-dimethylanilinium,N,N-dimethylbenzylammonium, N,N-dimethylcyclohexylammonium,

Suitable Lewis-acid cations are cations of the formula 12

[(Y^(a+))Q₁Q₂ . . . Q_(z)]^(d+)  (Formula 12)

where Y is an element of Groups 1 to 16 of the Periodic Table of theElements, Q₁ to Q_(z) are singly negatively charged groups such asC₁-C₂₈-alkyl, C₆-C₁₅-aryl, alkylaryl, arylalkyl, haloalkyl, haloaryleach having from 6 to 20 carbon atoms in the aryl radical and from 1 to28 carbon atoms in the alkyl radical, cycloalkyl groups of from 3 toabout 10 carbon atoms, which may in turn bear alkyl groups of from 1 toabout 10 carbon atoms as substitutents, halogen, alkoxy groups of from 1to 28 carbon atoms, aryloxy groups of from 6 to 15 carbon atoms, silylor mercaptyl groups.

a is an integer from 1-6,

z is an integer from 0 to 5 and

d corresponds to the difference a−z, but d is larger than or equal to 1

Particularly suitable cations are carbonium cations such astriphenylcarbenium, oxonium cations, sulfonium cations such astetrahydrothiophenium, phosphonium cations such as triethylphosphonium,triphenylphosphonium and diphenylphosphonium, and also cationictransition metal complexes such as the silver cation and the1,1′-dimethylferrocenium cation.

Preferred ionic compounds which can be used according to the presentinvention include:

-   triethylammoniumtetra(phenyl)borate,-   tributylammoniumtetra(phenyl)borate,-   trimethylammoniumtetra(tolyl)borate,-   tributylammoniumtetra(tolyl)borate,-   tributylammoniumtetra(pentafluorophenyl)borate,-   tributylammoniumtetra(pentafluorophenyl)aluminate,-   tripropylammoniumtetra(dimethylphenyl)borate,-   tributylammoniumtetra(trifluoromethylphenyl)borate,-   tributylammoniumtetra(4-fluorophenyl)borate,-   N,N-dimethylcyclohexylammoniumtetrakis(pentafluorophenyl)borate,-   N,N-dimethylbenzylammoniumtetrakis(pentafluorophenyl)borate-   N,N-dimethylaniliniumtetra(phenyl)borate,-   N,N-diethylaniliniumtetra(phenyl)borate,-   N,N-dimethylaniliniumtetrakis(pentafluorophenyl)borate,-   N,N-dimethylaniliniumtetrakis(pentafluorophenyl)aluminate,-   di(propyl)ammoniumtetrakis(pentafluorophenyl)borate,-   di(cyclohexyl)ammoniumtetrakis(pentafluorophenyl)borate,-   triphenylphosphoniumtetrakis(phenyl)borate,-   triethylphosphoniumtetrakis(phenyl)borate,-   diphenylphosphoniumtetrakis(phenyl)borate,-   tri(methylphenyl)phosphoniumtetrakis(phenyl)borate,-   tri(dimethylphenyl)phosphoniumtetrakis(phenyl)borate,-   triphenylcarbeniumtetrakis(pentafluorophenyl)borate,-   triphenylcarbeniumtetrakis(pentafluorophenyl)aluminate,-   triphenylcarbeniumtetrakis(phenyl)aluminate,-   ferroceniumtetrakis(pentafluorophenyl)borate and/or-   ferroceniumtetrakis(pentafluorophenyl)aluminate,

Preference is given totriphenylcarbeniumtetrakis(pentafluorophenyl)borate,N,N-dimethylcyclohexylammoniumtetrakis(pentafluorophenyl)borate orN,N-dimethylbenzylammoniumtetrakis(pentafluorophenyl)borate.

It is also possible to use mixtures of all of the above and belowmentioned cation-forming compounds. Preferred mixtures comprisealuminoxanes and an ionic compound, and/or a Lewis acid.

Other useful cocatalyst components are likewise borane or carboranecompounds such as

-   7,8-dicarbaundecaborane(13),-   undecahydrido-7,8-dimethyl-7,8-dicarbaundecaborane,-   dodecahydrido-1-phenyl-1,3-dicarbanonaborane,-   tri(butyl)ammoniumundecahydrido-8-ethyl-7,9-dicarbaundecaborate,-   4-carbanonaborane(14),-   bis(tri(butyl)ammonium)nonaborate,-   bis(tri(butyl)ammonium)undecaborate,-   bis(tri(butyl)ammonium)dodecaborate,-   bis(tri(butyl)ammonium)decachlorodecaborate,-   tri(butyl)ammonium-1-carbadecaborate,-   tri(butyl)ammonium-1-carbadodecaborate,-   tri(butyl)ammonium-1-trimethylsilyl-1-carbadecaborate,-   tri(butyl)ammoniumbis(nonahydrido-1,3-dicarbanonaborato)cobaltate(III),-   tri(butyl)ammoniumbis(undecahydrido-7,8-dicarbaundecaborato)ferrate(III).

The amount of Lewis acids or ionic compounds having Lewis-acid orBroensted-acid cations is preferably from 0.1 to 20 equivalents,preferably from 1 to 10 equivalents, based on the metallocene compoundof the formulas 1 or 1a.

Combinations of at least one Lewis base with bimetallic compounds of thetype R_(i) ¹⁷M³(-O-M³R_(j) ¹⁸)_(v) or R_(i) ¹⁸M³(-O-M³R_(j) ¹⁷)_(v)(formula 13), as described in Patent Application WO 99/40129, arelikewise important as cocatalyst systems.

In this regard, R¹⁷ and R¹⁸ are the same or different and represent ahydrogen atom, a halogen atom, a C₁-C₄₀ carbon-containing group,especially an alkyl group of from 1 to about 20 carbon atoms, haloalkylof from 1 to about 20 carbon atoms, alkoxy of from 1 to about 10 carbonatoms, aryl of from 6 to about 20 carbon atoms, haloaryl of from 6 toabout 20 carbon atoms, aryloxy of from 6 to about 20 carbon atoms,arylalkyl of from 7 to about 40 carbon atoms, haloarylalkyl of from 7 toabout 40 carbon atoms, alkylaryl of from 7 to about 40 carbon atoms, orhaloalkylaryl of from 7 to about 40 carbon atoms. R¹⁷ may also be an—OSiR⁵¹ ₃ group, in which the R⁵¹ groups are the same or different andhave the same meaning as R¹⁷, M³ is the same or different and representsan element of main group III of the periodic table of elements, i, j,and v each stands for a whole number 0, 1, or 2, and i+j+v is not equalto 0.

Preferred cocatalyst systems are the compounds of formulas (A) and (B)

where R¹⁷ and R¹⁸ have the same meaning as specified above.

Furthermore, compounds that are generally to be regarded as preferredare those formed by the reaction of at least one compound of formulas(C) and/or (D) and/or (E) with at least one compound of formula (F).

in which

-   R²⁷ may be a hydrogen atom or a boron-free C₁-C₄₀ carbon-containing    group, such as an alkyl of from 1 to about 20 carbon atoms, aryl of    from 6 to about 20 carbon atoms, arylalkyl of from 7 to about 40    carbon atoms, and alkylaryl of from 7 to about 40 carbon atoms, and    in which R¹⁷, R¹⁸ have the same meaning as specified above,-   D is an element of main Group VI of the periodic table of elements    or an NR⁶¹ group, where R⁶¹ is a hydrogen atom or a C₁-C₂₀    hydrocarbon group, such as alkyl of from 1 to about 20 carbon atoms    or aryl of from 6 to about 20 carbon atoms,-   f is a whole number from 0 to 3,-   g is a whole number from 0 to 3 where f+g corresponds to the valency    of Boron, and-   h is a whole number from 1 to 10.

The bimetallic compounds of formula 13 are possibly combined with anorganometallic compound of formula 14, i.e., [M⁴R¹⁹ _(q)]_(k), in whichM⁴ is an element of main Group I, II, or III of the periodic table ofthe elements, R¹⁹ is the same or different and represents a hydrogenatom, a halogen atom, a C₁-C₄₀ carbon-containing group, an alkyl groupof from 1 to about 20 carbon atoms, an aryl group of from about 6 toabout 40 carbon atoms, arylalkyl of from 7 to about 40 carbon atoms, andalkylaryl of from 7 to about 40 carbon atoms, q is a whole number from 1to 3, and k is a whole number from 1 to 4.

The organometallic compounds of formula 14 are preferably neutral Lewisacids, in which M⁴ stands for lithium, magnesium, and/or aluminum,especially aluminum. Examples of preferred organometallic compounds offormula 14 are trimethylaluminum, triethylaluminum,triisopropylaluminum, trihexylaluminum, trioctylaluminum,tri-n-butylaluminum, tri-n-propylaluminum, triisoprene aluminum,dimethyl aluminum monochloride, aluminum monochloride, diisobutylaluminum monochloride, methyl aluminum sesquichloride, ethyl aluminumsesquichloride, dimethyl aluminum hydride, aluminum hydride, diisopropylaluminum hydride, dimethyl aluminum(trimethylsiloxide), dimethylaluminum(triethylsiloxide), phenylalan, pentafluorophenylalan, ando-tolylalan.

The catalyst system of the invention contains an organoboroaluminumcompound, which contains units of formula 13, as the cocatalyticallyactive chemical compound. Compounds of formula 13 in which M³ stands forboron or aluminum are preferred. The compounds that contain units offormula 13 may be present as monomers or as linear, cyclic, or cage-likeoligomers. Two or more chemical compounds that contain units of formula13 may also form dimers, trimers, or higher combinations amongthemselves by Lewis acid-base interactions.

Preferred cocatalytically active bimetallic compounds correspond toformulas 15 and 16,

in which R¹⁰⁰ and R²⁰⁰ have the same meaning as the substituents R¹⁷ andR¹⁸ in formula 13.

Examples of the cocatalytically active compounds of formulas 15 and 16are

The compounds named in EP-A-924,223, DE 196 22 207.9, EP-A-601,830,EP-A-824,112, EP-A-824,113, WO 99/06,414, EP-A-811,627, WO 97/11,775, DE196 06 167.9 and DE 198 04 970 can be used as additional cocatalysts,which may be present in unsupported or supported form.

The amount of cocatalysts of formula 13 and/or 15 and/or 16 used in thecatalyst of the present invention can vary from 0.1 to 500 equivalents,preferably from 1 to 300 equivalents, most preferably from 5 to 150equivalents, based on the used amount of metallocene compound of theformulas 1 or 1a.

The catalyst system of the present invention can further comprise, asadditional component, a metal compound of the formula 17,

M⁵(R²²)_(r)(R²³)_(s)(R²⁴)_(t)  (Formula 17)

wherein

-   M⁵ is an alkali, an alkali earth metal or a metal of Group 13 of the    Periodic Table of the Elements,-   R²² is a hydrogen atom, alkyl of from 1 to about 10 carbon atoms,    aryl of from 6 to about 15 carbon atoms, or alkylaryl or arylalkyl    each having from 1 to 10 carbon atoms in the alkyl part and from 6    to 20 carbon atoms in the aryl part,-   R²³ and R²⁴ are each a hydrogen atom, a halogen atom, alkyl of from    1 to about 10 carbon atoms, C₆-C₁₅-aryl of from about 6 to about 15    carbon atoms, or alkylaryl, arylalkyl or alkoxy each having from 1    to 10 carbon atoms in the alkyl part and from 6 to 20 carbon atoms    in the aryl radical,-   r is an integer from 1 to 3 and s and t are integers from 0 to 2,    where the sum r+s+t corresponds to the valency of M⁵,    where this component is not identical with the above mentioned    cocatalyst compounds. It is also possible to use mixtures of various    metal compounds of the formula 17.

Among the metal compounds of the formula 17 preference is given to thosein which M⁵ is lithium, magnesium or aluminum and R²³ and R²⁴ are eachalkyl of from 1 to about 10 carbon atoms. Particularly preferred metalcompounds of the formula 17 are n-butyllithium,n-butyl-n-octyl-magnesium, n-butyl-n-heptylmagnesium,tri-n-hexylaluminum, triisobutylaluminum, triethylaluminum,trimethylaluminum or mixtures thereof.

If a metal compound of the formula 17 is used, it is preferably presentin the catalyst system in such an amount that the molar ratio of M⁵ tothe transition metal from the metallocene compound of formulas 1 or 1ais from 800:1 to 1:1, in particular from 200:1 to 2:1.

The support component of the catalyst system of the present inventioncan be any organic or inorganic inert solid or a mixture of such solids,in particulate porous solids such as hydrotalcites, talc, inorganicoxides and finely divided polymer powders.

Suitable inorganic oxides, which are preferably employed include fromthe Periodic Table of Elements Groups 1, 2, 3, 4, 5, 12, 13 and 14,metal oxides such as silicon dioxide, aluminum oxide, aluminosilicates,zeolites, MgO, ZrO₂, TiO₂ or B₂O₃, CaO, ZnO, ThO₂, Na₂O, K₂O, LiO₂ ormixed oxides like Al/Si oxides, Mg/Al oxides or Al/Mg/Si oxides. Othersuitable inorganic support materials are Na₂CO₃, K₂CO₃, CaCO₃, MgCl₂,Na₂SO₄, Al₂(SO₄)₃, BaSO₄, KNO₃, Mg(NO₃)₂ and Al(NO₃)₃.

Suitable polymer powders are homopolymers, copolymers, crosslinkedpolymers or polymer blends. Examples of such polymers are polyethylene,polypropylene, polybutene, polystyrene, divinylbenzene-crosslinkedpolystyrene, polyvinyl chloride, acrylonitrile-butadiene-styrenecopolymer, polyamide, polymethacrylate, polycarbonate, polyester,polyacetal or polyvinyl alcohol.

The preferred support materials have a specific surface area in therange from 10 to 1000 m²/g, a pore volume in the range from 0.1 to 5cm³/g and a mean particle size of from 1 to 500 μm. Preference is givento supports having a specific surface area in the range from 50 to 500m²/g, a pore volume in the range from 0.5 to 3.5 cm³/g and a meanparticle size in the range from 5 to 250 μm. Particular preference isgiven to supports having a specific surface area in the range from 200to 400 m²/g, a pore volume in the range from 0.8 to 3.0 cm³/g and a meanparticle size of from 10 to 100 μm.

The support materials can be thermally and/or chemically be pretreatedin order to adjust certain properties of the carrier such as the waterand/or the hydroxyl group content.

If the support material has a low moisture content or residual solventcontent, dehydration or drying before use can be omitted. If this is notthe case, as when using silica gel as support material, dehydration ordrying is advisable. Thermal dehydration or drying of the supportmaterial can be carried out under reduced pressure with or withoutsimultaneous inert gas blanketing (nitrogen). The drying temperature isin the range from 80° C. to 1000° C., preferably from 150° C. to 800° C.and most preferred from 150° C. to 400° C. The duration of the dryingprocess can be from 1 to 24 hours. But shorter or longer drying periodsare also possible.

In a preferred embodiment of the present invention, support materialswith a weight loss on dryness (LOD) of 0.5 wt. % or less, and even morepreferred with a LOD of 0.3 wt % or less are used. Higher amounts ofphysically adsorbed water up to 1 wt % are possible, but result inreduced catalyst activities. The loss on ignition (LOI) of the supportmaterial is preferably 1 wt % or greater or even more preferred between1.5 and 3.5 wt %. The weight loss on dryness (LOD) is thereby defined asthe weight loss between room temperature and 300° C. and the weight losson ignition (LOI) as the weight loss between 300° C. and 1000° C.

In addition or alternatively, dehydration or drying of the supportmaterial can also be carried out by chemical means, by reacting theadsorbed water and/or the surface hydroxyl groups with suitablepassivating agents. Reaction with the passivating reagent can convertthe hydroxyl groups completely or partially into a form, which does notshow any adverse interaction with the catalytically active centers.Suitable passivating agents are silicon halides, silanes or amines, eg.silicon tetrachloride, chlorotrimethylsilane, dichlorodialkylsilanes,dimethylaminotrichlorosilane, N,N-dimethylanilin orN,N-dimethylbenzylamine or organometallic compounds of aluminum, boronand magnesium, eg. aluminoxanes, trimethylaluminum, triethylaluminum,triisobutylaluminum, diisobutylaluminum hydride, triethylborane ordibutylmagnesium.

As outlined above, organic support materials such as finely dividedpolymer powders, can also be used and should, before use, likewise befreed from any adhering moisture, solvent residues or other impuritiesby means of appropriate purification and drying operations.

Preference is given to using silica gels having the defined parametersas support materials. Spray dried silica grades, which inherentlyexhibit meso and macro pores, cavities and channels are preferred overgranular silica grades.

The supported catalyst system according to this invention can be made invarious ways.

In one embodiment of the present invention, at least one of theabove-described metallocene components of formulas 1 or 1a is broughtinto contact in a suitable solvent with at least one cocatalystcomponent, preferably giving a soluble reaction product, an adduct or amixture. The obtained composition is mixed with the dehydrated orpassivated support material, the solvent is removed and the resultingsupported metallocene catalyst system is dried to ensure that thesolvent is completely or mostly removed from the pores of the supportmaterial. The supported catalyst is obtained as a free-flowing powder.

As an example, the process for preparing a free-flowing and, if desired,prepolymerized supported catalyst system comprises the following steps:

a) preparing a metallocene/cocatalyst mixture in a suitable solvent orsuspension medium, where the metallocene component has one of theabove-described structures,

b) applying the metallocene/cocatalyst mixture to a porous, preferablyinorganic, if necessary thermally or chemically pretreated support,

c) removing the major part of solvent from the resulting mixture,

d) isolating the supported catalyst system and

e) if desired, prepolymerizing the resulting supported catalyst systemwith one or more olefinic monomer(s), to obtain a prepolymerizedsupported catalyst system.

In another embodiment of this invention the metallocene/cocatalystcomposition is mixed with the dehydrated or passivated support material,the supported catalyst is recovered and optionally washed with anaromatic hydrocarbon and/or paraffinic hydrocarbon solvent. The isolatedcatalyst is then dispersed in a non-reactive suspension media such as aparaffinic hydrocarbon solvent, a mineral oil or a wax of mixturesthereof.

In a further embodiment of this invention the catalyst is preparedaccording to the procedure disclosed in WO 06/60544, WO 00/05277 and WO98/01481.

As an example, in WO 06/60544, a free flowing and, if desired,prepolymerized supported catalyst system is prepared comprising thefollowing steps:

a) contacting at least one support material with a first portion of atleast one co-catalyst in a suitable solvent

b) impregnating the co-catalyst loaded support with a suspension orsolution, which comprises at least one metallocene and a second portionof at least one co-catalyst in a suitable solvent

c) isolating the supported catalyst system and

f) if desired, prepolymerizing the resulting supported catalyst systemwith one or more olefinic monomer(s), to obtain a prepolymerizedsupported catalyst system.

Thus, as an example, the process according to WO 06/60544 for preparinga free-flowing and, if desired, prepolymerized supported catalyst systemcomprises the following steps:

a) Contacting a support material with a first composition which includesat least one aluminoxane in a first solvent at a temperature of about 10to 30° C. followed by keeping the mixture at about 20° C. for 0 to 12hours, subsequently heating the resulting mixture to a temperature of 30to 200° C. and keeping the mixture at 30 to 200° C. for 30 minutes to 20hours, optionally followed by removing all or part of the first solventand/or optionally followed by one or more washing step(s) using asuitable solvent,

b) Suspending and/or dissolving, respectively, at least one metalloceneof formula 1 and/or 1a and a second portion of an aluminoxane or of amixture of aluminoxanes or of an ionic compound and/or a Lewis acid in asecond solvent or suspension medium at a temperature of 0 to 100° C.,optionally followed by a preactivation time of 1 minute to 200 hours ata temperature of 10 to 100°,

c) Applying the mixture prepared in b) to the aluminoxane loaded supportmaterial produced in a), at a temperature of 10 to 100° C. and a contacttime of 1 minute to 24 hours,

d) Removing the major part of the solvent from the resulting mixture andoptionally washing the resulting supported catalyst with a suitablesolvent,

e) Isolating the supported catalyst system and

f) Optionally prepolymerizing the resulting supported catalyst systemwith one or more olefinic monomer(s), to obtain a prepolymerizedsupported catalyst system.

More specifically, as an example, the process according to WO 06/60544for preparing a free-flowing and, if desired, prepolymerized supportedcatalyst system comprises the following steps:

the process for preparing a free-flowing supported catalyst systemaccording to the present invention comprises the following steps:

a) Contacting a support material with a first composition which includesat least 5 mmol of an aluminoxane or of a mixture of aluminoxanes per gsupport material in a first solvent at a temperature of about 20° C.followed by keeping the mixture at about 20° C. for 0.15 to 2 hours,subsequently heating the resulting mixture to a temperature of 50 to160° C. and keeping the mixture at 50 to 160° C. for 1 to 6 hours,optionally followed by removing all or part of the first solvent and/oroptionally followed by one or more washing step(s) using a suitablesolvent,

b) Suspending and/or dissolving, respectively, at least 0.5 mmole of asecond portion of an aluminoxane or of a mixture of aluminoxanes per gsupport material and at least 0.1 mol % of the employed second portionof an aluminoxane or of a mixture of aluminoxanes per g support materialof at least one metallocene of formula 1 and/or 1a in a second solventor suspension medium at a temperature of 20 to 50° C., optionallyfollowed by a preactivation time of 1 minute to 200 hours at atemperature of 20 to 30°,

c) Applying the mixture prepared in b) to the aluminoxane loaded supportmaterial produced in a), at a temperature of 10 to 100° C. and a contacttime of 1 minute to 24 hours,

d) Removing the major part of the solvent from the resulting mixture and

e) Optionally washing the resulting supported catalyst with a suitablesolvent, and/or drying the resulting supported catalyst at temperaturesof 30 to 60° C., and

f) Optionally prepolymerizing the resulting supported catalyst systemwith one or more olefinic monomer(s), to obtain a prepolymerizedsupported catalyst system.

In a preferred embodiment, as an example, the process according to WO06/60544 for preparing a free-flowing and, if desired, prepolymerizedsupported catalyst system comprises the following steps:

a) Contacting an optionally thermally pretreated silica support materialwith at least 10 mmol of an aluminoxane per g support material intoluene at a temperature of about 20° C. followed by subsequentlyheating the resulting mixture to a temperature of 50 to 110° C. andkeeping the mixture at 50 to 110° C. for 1 to 6 hours, optionallyfollowed by removing all or part of the toluene, and/or optionallyfollowed by one or more washing step(s) using a suitable solvent,

b) Suspending and/or dissolving, respectively, at least 0.5 mmole of asecond portion of an aluminoxane per g support material and at least 0.1mol % of the employed second portion of an aluminoxane or of a mixtureof aluminoxanes per g support material of at least one metallocene offormula 1 and/or 1a in toluene at a temperature of 20 to 50° C.,optionally followed by a preactivation time of 1 minute to 200 hours ata temperature of 20 to 30°,

c) Applying the mixture prepared in b) to the aluminoxane loaded supportmaterial produced in a), at a temperature of 10 to 100° C. and a contacttime of 1 minute to 24 hours,

d) Removing the major part of the toluene from the resulting mixture and

e) Optionally washing the resulting supported catalyst with a suitablesolvent, and/or drying the resulting supported catalyst at temperaturesof 30 to 60° C., and

f) Optionally prepolymerizing the resulting supported catalyst systemwith one or more olefinic monomer(s), to obtain a prepolymerizedsupported catalyst system.

In a more preferred embodiment, as an example, the process according toWO 06/60544 for preparing a free-flowing and, if desired, prepolymerizedsupported catalyst system comprises the following steps:

a) Contacting an optionally thermally pretreated silica support materialwith a weight loss on dryness (LOD) of 0.5 wt. % or less and a weightloss on ignition (LOI) of 1.0 wt. % or greater with a first compositionwhich includes at least 10 mmol of methylaluminoxane per g supportmaterial in toluene at a temperature of about 20° C. followed bysubsequently heating the resulting mixture to a temperature of 110° C.and keeping the mixture at 110° C. for 1 to 6 hours, optionally followedby removing all or part of the toluene, and/or optionally followed byone or more washing step(s) using a suitable solvent,

b) Suspending and/or dissolving, respectively, at least 1 mmole of asecond portion of methylaluminoxane per g support material and at least0.1 mol % of the employed second portion of methylaluminoxane per gsupport material of at least one metallocene of formula 1 and/or 1a intoluene at a temperature of 20 to 50° C., optionally followed by apreactivation time of 1 minute to 200 hours at a temperature of 20 to30°,

c) Applying the mixture prepared in b) to the methylaluminoxane loadedsupport material produced in a), by passing the impregnation suspensionor solution b) through the methylaluminoxane loaded support material ina direct flow or by using an incipient wetness impregnation technique,where the volume of the impregnation suspension or solution or the totalliquid volume used in the impregnation step, respectively, does notexceed 250% of the total pore volume of the support material, at atemperature of 10 to 100° C. and a contact time of 1 minute to 24 hours,

d) Removing the major part of the toluene from the resulting mixture and

e) Optionally washing the resulting supported catalyst with a suitablesolvent, and/or drying the resulting supported catalyst at temperaturesof 30 to 60° C., and

f) Optionally prepolymerizing the resulting supported catalyst systemwith one or more olefinic monomer(s), to obtain a prepolymerizedsupported catalyst system.

In a particular preferred embodiment, as an example, the processaccording to WO 06/60544 for preparing a free-flowing and, if desired,prepolymerized supported catalyst system comprises the following steps:

a) Contacting an optionally thermally pretreated silica support materialwith a weight loss on dryness (LOD) of 0.3 wt. % or less and a weightloss on ignition (LOI) between 1.5 and 3.5 wt. %, with at least 10 mmolof methylaluminoxane per g support material in toluene at a temperatureof about 20° C. followed by subsequently heating the resulting mixtureto a temperature of 110° C. and keeping the mixture at 110° C. for 1 to6 hours, optionally followed by removing all or part of the toluene,and/or optionally followed by one or more washing step(s) using asuitable solvent,

b) Suspending and/or dissolving, respectively, at least 1 mmole of asecond portion of methylaluminoxane per g support material and at least0.1 mol % of the employed second portion of methylaluminoxane per gsupport material of at least one metallocene of formula 1a in toluene ata temperature of 20 to 50° C., optionally followed by a preactivationtime of 1 minute to 200 hours at a temperature of 20 to 30°,

c) Applying the mixture prepared in b) to the methylaluminoxane loadedsupport material produced in a), by passing the impregnation suspensionor solution b) through the aluminoxane loaded support material a) in adirect flow or by using an incipient wetness impregnation technique,where the volume of the impregnation suspension or solution or the totalliquid volume used in the impregnation step, respectively, does notexceed 250% of the total pore volume of the support material, at atemperature of 10 to 100° C. and a contact time of 1 minute to 24 hours,

d) Removing the major part of the toluene from the resulting mixture and

e) Optionally washing the resulting supported catalyst with a suitablesolvent, and/or drying the resulting supported catalyst at temperaturesof 30 to 60° C., and

f) Optionally prepolymerizing the resulting supported catalyst systemwith one or more olefinic monomer(s), to obtain a prepolymerizedsupported catalyst system.

According to the present invention, for preparing a free-flowing and, ifdesired, prepolymerized supported catalyst system, in step b) of thecatalyst preparations as mentioned above, instead of an aluminoxane or amixture of aluminoxanes, at least one alkyl compound of elements of mainGroups I to III of the Periodic Table, for example a magnesium alkyl, alithium alkyl or an aluminum alkyl like trimethylaluminum,triethylaluminum, triisobutylaluminum, triisopropylaluminum,trihexylaluminum, trioctylaluminum, tri-n-butylaluminum,tri-n-propylaluminum, triisoprene aluminum, dimethyl aluminummonochloride, aluminum monochloride, diisobutyl aluminum monochloride,methyl aluminum sesquichloride, ethyl aluminum sesquichloride, dimethylaluminum hydride, aluminum hydride, diisopropyl aluminum hydride,dimethyl aluminum(trimethylsiloxide), dimethylaluminum(triethylsiloxide), phenylalan, pentafluorophenylalan, ando-tolylalan, can be used. Preferred aluminum alkyls aretrimethylaluminum, triethylaluminum, triisobutylaluminum.

In an even further embodiment of the present invention a free flowingand, if desired, prepolymerized supported catalyst system is preparedcomprising the following steps:

a) preparing a trialkylaluminum/borinic acid mixture in a suitablesolvent or suspension medium

b) applying the trialkylaluminum/borinic acid mixture to a porous,preferably inorganic, if necessary thermally or chemically pretreatedsupport, which was prior treated with a base likeN,N-diethylbenzylamine, N,N-dimethylbenzylamine, N-benzyldimethylamine,N-benzyldiethylamine, N-benzylbutylamine, N-benzyl tertbutylamine,N-benzylisopropylamine, N-benzylmethylamine, N-benzylethylamine,N-benzyl-1-phenylethylamine, N-benzyl-2-phenylethylamine,N,N-dimethylbenzylamine, N,N-diethylbenzylamine,N-methyl-N-ethylbenzylamine, N-methyldibenzylamine andN-ethyldi(benzyl)amine,

c) removing the major part of solvent from the resulting mixture toobtain a supported cocatalyst,

d) preparing a metallocene/supported cocatalyst mixture in a suitablesolvent or suspension medium, where the metallocene component has one ofthe above-described structures,

e) isolating the supported catalyst system and

f) if desired, prepolymerizing the resulting supported catalyst systemwith one or more olefinic monomer(s), to obtain a prepolymerizedsupported catalyst system.

Preferred solvents for the preparation of the metallocene/cocatalystmixture are hydrocarbons and hydrocarbon mixtures, which are liquid atthe selected reaction temperature and in which the individual componentspreferably dissolve. The solubility of the individual components is,however, not a prerequisite as long as it is ensured that the reactionproduct of metallocene and cocatalyst components is soluble in thesolvent selected. Suitable solvents are alkanes such as pentane,isopentane, hexane, isohexane, heptane, octane and nonane, cycloalkanessuch as cyclopentane and cyclohexane and aromatics such as benzene,toluene, ethylbenzene and diethylbenzene. Very particular preference isgiven to toluene, heptane and ethylbenzene.

For a preactivation, the metallocene in the form of a solid is dissolvedin a solution of the cocatalyst in a suitable solvent. It is alsopossible to dissolve the metallocene separately in a suitable solventand subsequently to combine this solution with the cocatalyst solution.Preference is given to using toluene. The preactivation time is from 1minute to 200 hours. The preactivation can take place at roomtemperature of 25° C. In individual cases, the use of highertemperatures can reduce the required preactivation time and give anadditional increase in activity. Elevated temperatures in this caserefer to a range from 25° C. to 100° C.

The preactivated solution or the metallocene/cocatalyst mixture issubsequently combined with an inert support material, usually silicagel, which is in the form of a dry powder or as a suspension in one ofthe above mentioned solvents. The support material is preferably used aspowder. The preactivated metallocene/cocatalyst solution or themetallocene/cocatalyst mixture can be either added to the initiallycharged support material, or else the support material can be introducedinto the initially charged solution.

The volume of the preactivated solution or the metallocene/cocatalystmixture can exceed 100% of the total pore volume of the support materialused or else be up to 100% of the total pore volume.

The temperature at which the preactivated solution or themetallocene/cocatalyst mixture is brought into contact with the supportmaterial can vary within the range from 0° C. to 100° C. However, loweror higher temperatures are also possible.

While the solvent is completely or mostly removed from the supportedcatalyst system, the mixture can be stirred and, if desired, alsoheated. Preferably, both the visible portion of the solvent and theportion in the pores of the support material are removed. The removal ofthe solvent can be carried out in a conventional way using reducedpressure and/or purging with inert gas. During the drying process, themixture can be heated until the free solvent has been removed, whichusually takes from 1 to 3 hours at a preferred temperature of from 30°C. to 60° C. The free solvent is the visible portion of the solvent inthe mixture. For the purposes of the present invention, residual solventis the portion present in the pores.

As an alternative to the complete removal of the solvent, the supportedcatalyst system can also be dried until only a certain residual solventcontent is left, with the free solvent having been completely removed.Subsequently, the supported catalyst system can be washed with alow-boiling hydrocarbon such as pentane or hexane and dried again.

The supported catalyst system prepared according to the presentinvention can be used either directly for the polymerization of olefinsor be prepolymerized with one or more olefinic monomers, with or withoutthe use of hydrogen as molar mass regulating agent, prior to use in apolymerization process. The procedure for the prepolymerization ofsupported catalyst systems is described in WO 94/28034.

As additive, it is possible to add, during or after the preparation ofthe supported catalyst system, a small amount of an olefin, preferablyan alpha-olefin such as styrene or phenyldimethylvinylsilane asactivity-increasing component or an antistatic, as described in U.S.Ser. No. 08/365,280. The molar ratio of additive to metallocenecomponent of formulas 1 or 1a is preferably from 1:1000 to 1000:1, veryparticularly preferably from 1:20 to 20:1.

The present invention also provides a process for preparing a polyolefinby polymerization of one or more olefins in the presence of the catalystsystem of the present invention comprising at least one transition metalcomponent of the formulas 1 or 1a. For the purposes of the presentinvention, the term polymerization refers to both homopolymerization andcopolymerization and the term copolymerization includesterpolymerisation or copolymerisation of more than three differentmonomers.

Preference is given to polymerizing olefins of the formulaR^(m)—CH═CH—R^(n), where R^(m) and R^(n) are identical or different andare each a hydrogen atom or a radical having from 1 to 20 carbon atoms,in particular from 1 to 10 carbon atoms, and R^(m) and R^(n) togetherwith the atoms connecting them can form one or more rings.

Suitable olefins are 1-olefins, eg. ethene, propene, 1-butene,1-pentene, 1-hexene, 4-methyl-1-pentene or 1-octene, styrene, dienessuch as 1,3-butadiene, 1,4-hexadiene, vinylnorbornene, norbornadiene,ethylnorbornadiene and cyclic olefins such as norbornene,tetracyclododecene or methylnorbornene. In the process of the presentinvention, preference is given to homopolymerizing propene or ethene orcopolymerizing propene with ethene and/or one or more 1-olefins havingfrom 4 to 20 carbon atoms, eg. 1-butene or hexene, and/or one or moredienes having from 4 to 20 carbon atoms, eg. 1,4-butadiene,norbornadiene, ethylidenenorbornene or ethylnorbornadiene. Very suitablecopolymers are ethene-propene copolymers, propene-1-pentene copolymersand ethene-propene-1-butene, ethene-propene-1-pentene orethene-propene-1,4-hexadiene terpolymers.

The polymerization is carried out at from −60° C. to 300° C., preferablyfrom 50° C. to 200° C., very particularly preferably from 50° C. to 95°C. The pressure is from 0.5 to 2000 bar, preferably from 5 to 100 bar.

The polymerization can be carried out in solution, in bulk, insuspension or in the gas phase, continuously or batchwise, in one ormore stages. As an example, impact copolymers are preferably produced inmore than one stage. The homopolymer or random copolymer content of sucha polymer can be produced in (a) first stage(s) and the copolymer rubbercontent can be produced in (a) consecutive stage(s).

The supported catalyst system prepared according to the presentinvention can be used as sole catalyst component for the polymerizationof olefins or preferably in combination with at least one alkyl compoundof elements of main Groups I to III of the Periodic Table, for examplean aluminum alkyl, magnesium alkyl or lithium alkyl or an aluminoxane.The alkyl compound is added to the monomer or suspension medium andserves to free the monomer of substances, which can impair the catalyticactivity. The amount of alkyl compound added depends on the quality ofthe monomers used.

To prepare olefin polymers having a broad or bimodal molecular weightdistribution or a broad or bimodal melting range, it is recommended touse a catalyst system comprising two or more different metallocenesand/or two or more different cocatalysts. Alternatively two or moredifferent catalyst systems of the present invention can be used as amixture.

As molar mass regulator and/or to increase the activity, hydrogen isadded if required.

The catalyst system may be supplied to the polymerization system as asolid or in the form of a paste or suspension in a hydrocarbon or may betreated with inert components, such as paraffins, oils, or waxes, toachieve better metering. If the catalyst system is to be metered intothe reactor together with the monomer to be polymerized or the monomermixture to be polymerized, the mixing unit and the metering line arepreferably cooled.

Furthermore, an additive such as an antistatic or an alcohol can be usedin the process of the present invention, for example to improve theparticle morphology of the olefin polymer. In general it is possible touse all antistatics which are suitable in olefin polymerizationprocesses. It is preferred to dose the antistatic directly into thepolymerization system, either together with or separately from thecatalyst system used.

The polymers prepared using the catalyst systems of the presentinvention display an uniform particle morphology and contain no fines.No agglomerates or deposits are obtained in the polymerization using thecatalyst system of the present invention.

The catalyst systems of the present invention give polymers such aspolypropylene having high molecular weight and cover a broad range ofstereospecificity and regiospecificity.

The copolymers which can be prepared using the catalyst system based onmetallocenes of formula 1 or 1a of the present invention have asignificantly higher molar mass compared to the prior art. At the sametime, such copolymers can be prepared using the catalyst system of thepresent invention at a high productivity and at industrially relevantprocess parameters without deposit formation.

The polymers prepared by the process of the present invention aresuitable, in particular, for producing products such as fibers,filaments, injection-molded parts, films, sheets, caps, closures,bottles or large hollow bodies such as pipes with excellent properties.

EXAMPLES General Procedures

The preparation and handling of the organometallic compounds werecarried out under argon using Schlenk techniques or in a glove box. Allsolvents were purged with argon and dried over molecular sieves beforeuse.

The metallocenes produced were characterized by ¹H-NMR spectroscopyusing a Bruker DMX 500 spectrometer, operating at 500 MHz using CDCl₃ asthe solvent.

The polymers produced were characterized by ¹H-NMR, ¹³C-NMR, DSC, GPC,TREF/ATREF, Melt Flow Rate and IR spectroscopy.

1. Gel Permeation Chromatography (GPC), Determination of Mw and Mw/Mn

A Waters Alliance/GPCV2000 equipped with a refractometer, a triplecapillary on-line viscometer (Waters Corporation, 34 Maple Street,Milford, Mass., 01757 USA) and a light scattering detector PD 2040(Precision Detectors Inc., 34 Williams Way, Bellingham, Mass., USA) wasused for the determination of the molar mass data of the samples. 0.05wt % solutions of the samples in 1,2,4-trichlorobenzene were analyzed ata temperature of 145° C. using a Mixed B light scattering quality column(Polymer Labs 1110-6100LS) and a Mixed B guard column (Polymer Labs1110-1120). Weight average molar mass (Mw) and the ratio of weightaverage molar mass to number average molar mass (Mw/Mn) were calculatedusing the Cumulative Matching. % Broad Standard procedure that isavailable in the Waters Millenium 3.2 GPC software module.

2. NMR Spectroscopy

Samples were prepared by weighing 0.32 g of polymer into 2.5 ml of a1,2,4-trichlorobenzene/deuterobenzene-d6 (4:1 volume) mixture. Sampleswere heated to 125° C. and mixed until a homogeneous solution was formed(typically 1-4 hours). Spectra were obtained at 120° C. on a VarianInova 500 instrument (Varian Inc., 3120 Hansen Way, Palo Alto, Calif.,94304, USA) operating at a ¹³C-spectrometer frequency of 125.7 MHz andusing a 10 mm probe. Spectra were obtained using 5000 scans employing aπ/2 pulse of 10.0 μs, a recycle delay of 10.0 s and an acquisition timeof 2.5 s. Waltz-16 decoupling remained on throughout the pulse sequenceto gain the signal to noise enhancement due to the effects of nOe.Spectra were processed with 1 Hz of line broadening. The mmmm peak inthe methyl region of the spectrum was used as an internal chemical shiftreference and was set to 21.85 ppm.

3. Differential Scanning Calorimetry (DSC), Determination of the PolymerMelting Point Tm

DSC measurements were carried out using a Mettler Toledo DSC 822e(Mettler-Toledo Inc., 1900 Polaris Parkway, Columbus, Ohio, 43240, USA).4 mg of sample were weighed into a standard aluminum pan and subjectedto the following temperature schedule:

The samples were heated from room temperature to 220° C. at a heatingrate of 20° C./min, maintained at this temperature for 5 min, thencooled down to −55° C. at a cooling rate of 20° C./min, maintained atthe same temperature for 5 min, then heated to 220° C. at a heating rateof 20° C./min. The melting point was determined from the second heatingrun as the temperature where the main peak was observed in the curve.

4. Analytical TREF (ATREF)

The TREF experiment is carried out on a TREF system built from amodified Waters 2000CV instrument (Waters Corporation, 34 Maple Street,Milford, Mass., 01757 USA). The 2000CV instrument is maintained at 140°C. in o-dichlorobenzene (ODCB) solvent at 1 ml/min flowrate. To detectthe polyolefin fractions eluting from the TREF column, the system uses aheated infrared IR⁴ detector (PolymerChar Company, Valencia TechnologyPark, P.O. Box 176, Valencia, Va., E-46980, PATERNA, Spain). For coolingand heating of the TREF column, the system uses atemperature-programmable HAAKE Phoenix II oil bath (Thermo ElectronCorporation, 401 Millcreek Road, Marietta, Ohio 45750, USA). The TREFseparation column is a stainless steel column of 100 mm long and 0.75 mmdiameter packed with 20-micrometer cross-linked polystyrene beads. ThisTREF column is maintained at the 140° C. temperature in the oil bathbefore the sample analyses. Polymer samples are dissolved in ODCBsolvent at 140° C. at a concentration of 2 mg/ml. One ml of the testsample of the resultant ODCB solution is injected into the TREF columnby the auto-injection system of the Waters 2000CV instrument with aflowrate of ODCB set at 1 ml/min. Following the sample injection, theODCB flow is diverted away from the TREF column. As the sample is keptinside the column, the column is allowed to cool down in the oil bathfrom 140° C. down to 0° C. at the cooling rate of 1.5° C./min. In thiscooling step, the polymer molecules in the test sample are precipitatedonto the packing beads in the TREF column. While the column is still at0° C. temperature, a flow of hot ODCB at 1 ml/min is re-introduced tothe TREF column for 2 minutes to elute the soluble fraction of thepolymer sample and detected by the IR detector set at 3.4 micrometerwavelength. Then, the temperature is raised at a heating rate of 2°C./min while the ODCB flow is maintained at 1 ml/min through the TREFcolumn to elute the higher melting polymer fractions which are beingdetected on-line by the IR⁴ detector.

5. Melt Flow Rate (MFR)

The MFR of the samples were determined according to ISO 1133 at 230° C.Two different loads were used: 2.16 kg and 5 kg. Values are reported asMFR(230/2.16) and MFR(230/5), respectively.

6. Productivity

The productivity of a catalyst is determined by dividing the producedmass of polypropylene by the mass of catalyst used and the reactiontime.

7. Yield

The yield of a sample is determined by dividing the isolated amount ofthe desired product divided by the theoretical achievable amount of theproduct.

The following abbreviations are employed:

-   PP=polypropylene-   MC=metallocene-   Cat=supported catalyst system-   h=hour-   T_(g)=glass transition temperature in ° C., determined by    differential scanning calorimetry (DSC, conditions see above)

Synthesis of Metallocenes Example 1Dimethylsilandiyl-bis-(2-(cyclohexylmethyl)-4-(4′-tert-butylphenyl)-1-indenyl)-zirconiumdichloride (2-Bromo-ethyl)-cyclohexane

In a 1 l-roundbottom flask equipped with a reflux condenser 164 gconcentrated sulphuric acid and 200 g hydrobromic acid (48% in water)were added subsequently under cooling with an ice bath to 88.7 g (0.693mole) 2-cyclohexyl-ethanol. The mixture was refluxed for 6 h and aftercooling to room temperature given to 400 g of ice. The aqueous phase wasextracted with 400 ml pentane. The organic layer was washed with a 2 MNaOH-solution and with water, dried over magnesium sulphate, and thesolvent was removed in vacuo. The product was distilled in vacuo toyield 112.7 g (85%) of (2-bromo-ethyl)-cyclohexane as a colourless oil.¹H-NMR (400 MHz, CDCl₃): δ=3.40 (2H, t, CH₂Br), 1.73-1.61 (m, 7H), 1.44(m, 1H), 1.26-1.11 (m, 3H), 0.92-0.84 (m, 2H) ppm.

1-(2-Chloro-phenyl)-3-cyclohexyl-propan-1-one

15.57 g (640 mmole) Magnesium turnings were placed in a 1 l-roundbottomflask equipped with a dropping funnel and a reflux condenser, and 50 mlof THF were added. The magnesium was etched slightly with a few crystalsof iodine and then 2 g of (2-bromo-ethyl)-cyclohexane were added and themixture was heated locally. After the start of the Grignard-formationthe rest of the (2-bromo-ethyl)-cyclohexane in 350 ml of THF (112.65 gin total, 589 mmole) were added within a period of 20 min. The mixturewas refluxed for 1.5 h and then cooled to room temperature. In aseparate 2 l-roundbottom flask 70.5 g (513 mmole) of2-chloro-benzonitrile and 156 mg (0.16 mole %) copper(I)iodide weredissolved in 130 ml of THF. The Grignard-solution was added dropwiseover a period of 30 min and the reaction mixture was refluxed for 3 h.After standing overnight at room temperature, a mixture of 190 ml waterand 127 ml concentrated hydrochloric acid were added very carefully,causing a strongly exothermic reaction. The mixture was stirred at 50°C. for 1 h and the layers were separated. The aqueous layer wasextracted twice with 150 ml of toluene each. The combined organic layerswere washed twice with 2 M sulphuric acid, once with a saturated sodiumbicarbonate solution and once with a saturated sodium chloride solution.After drying over magnesium sulphate the solvent was evaporated in vacuoto yield 133.5 g (quant.) of the desired phenone as slightly brown oil.¹H-NMR (400 MHz, CDCl₃): δ=7.41-7.14 (m, 4H, aromatic), 2.91 (t, 2H,COCH₂), 1.71-1.55, 1.28-1.10, 0.93-0.85 (3×m, 13H) ppm.

7-Chloro-2-cyclohexylmethyl-indan-1-one

66 g (263 mmole) 1-(2-Chloro-phenyl)-3-cyclohexyl-propan-1-one, 77.5 g(2.1 eq.) urotropine and 72.6 g (2.7 eq.) of acetic anhydride wereplaced in a 500 ml roundbottom flask and the mixture was stirred at 80°C. for 4 h. Then 100 ml water and 100 ml 2M NaOH were added and themixture was extracted two times with 200 ml dichloromethane each. Theorganic layer was washed two times with 100 ml saturated aqueousammonium chloride and dried over magnesium sulphate. The solvent amountwas reduced in vacuo to a total of 150 ml volume and the solution wasadded dropwise over a period of 2.5 h to 660 g of hot (70-75° C.)concentrated sulphuric acid. After stirring for an additional 30 min at75° C. the mixture was allowed to stand overnight at room temperature.The mixture was given to approx. 500 g of ice and extracted three timeswith 150 ml dichloromethane each. The organic layer was washed twicewith 150 ml of a saturated sodium bicarbonate solution and once with 100ml of a saturated sodium chloride solution. After drying over magnesiumsulphate the solvent was removed in vacuo. The product was purified bycolumn chromatography on silica (heptane/dichloromethane 5:1) to yield40.0 g (61%) of the desired product as a slightly off-white oil, whichslowly crystallized. ¹H-NMR (400 MHz, CDCl₃): δ=7.42 (t, 1H, aromatic),7.29 (d, 1H, aromatic), 7.24 (d, 1H, aromatic), 3.25 (dd, 1H, COCH),2.71 (m, 2H, benzylic), 1.78-0.87 (m, 13H, aliphatic) ppm.

7-(4′-tert-Butyl-phenyl)-2-cyclohexylmethyl-indan-1-one

60 g (228 mmole) 7-Chloro-2-cyclohexylmethyl-indan-1-one, 49 g (1.2 eq.)4-tert-butyl-benzene boronic acid, 53 g sodium carbonate, 750 mlethylene glycol and 150 ml water were placed in a 2 l-roundbottom flaskequipped with a mechanical stirrer and a reflux condenser. The mixturewas degassed three times by slight evacuation and recharging with argon.A premixed catalyst solution consisting of 103 mg (0.2 mole %) palladiumacetate, 3 ml NaTPPTS (2.6 M in water, 0.8 mole %) and 2 ml of water wasadded and the mixture was refluxed at 125° C. until complete conversion(approx. 4 h). 300 ml of water were added and the mixture was extractedthree times with 150 ml of toluene each. The combined organic layerswere washed twice with 100 ml water and once with 100 ml of a saturatedsodium chloride solution. Drying over magnesium sulphate and evaporationof the solvent in vacuo yielded 87.2 g (quant.) of the desired productas a yellow sticky oil. ¹H-NMR (400 MHz, CDCl₃): δ=7.54 (t, 1H,aromatic), 7.43, 7.38 (2×d, 4H, aromatic), 7.24 (m, 2H, aromatic), 3.30(m, 1H, COCH), 2.80-2.67 (3×m, 2H, benzylic), 1.85-1.47 (m, 7H,aliphatic), 1.35 (s, 9H, C(CH₃)₃), 1.27-0.87 (m, 6H, aliphatic) ppm.

7-(4′-tert-Butyl-phenyl)-2-cyclohexylmethyl-1H-indene

82.3 g (229 mmole)7-(4′-tert-Butyl-phenyl)-2-cyclohexylmethyl-indan-1-one were dissolvedin 292 ml toluene in a 1 l-roundbottom flask equipped with a refluxcondenser. 9.5 g (1.1 eq.) sodium borohydride were added. Then 40 ml(4.3 eq.) methanol were added at 50° C. and the mixture was stirred for3 h at 50° C. An additional 1 g of sodium borohydride and 5 ml methanolwere added and the mixture was stirred another 2 h at 50° C. 2Msulphuric acid was added until the gas evolution ceased. After additionof 100 ml water the layers were separated and the organic layer waswashed two times with 2M sulphuric acid and once with a saturated sodiumchloride solution. The solvent was evaporated and the crude indanol wasdissolved in approx. 350 ml of toluene. After addition of 0.7 gp-toluene sulfonic acid the mixture was heated to reflux using aDean-Stark-trap until TLC showed complete conversion (90 min). Thesolution was washed twice with a saturated NaHCO₃-solution, once withwater and once with a saturated sodium chloride solution. Drying overmagnesium sulphate, evaporation of the solvent and crystallization from800 ml ethanol afforded 67.3 g (86%) of the desired indene as whitecrystals. ¹H-NMR (400 MHz, CDCl₃): δ=7.45, 7.33, 7.25, 7.14 (4×m, 7H,aromatic), 6.69 (s, 1H, ═CH), 3.35 (s, 2H, benzylic), 2.34 (d, 2H,aliphatic), 1.71-1.50 (m, 6H, aliphatic), 1.39 (s, 9H, C(CH₃)₃),1.24-0.87 (m, 5H, aliphatic) ppm.

Dimethylsilandiyl-bis-(2-(cyclohexylmethyl)-4-(4′-tert-butylphenyl)-1-indenyl)-zirconiumdichloride

20 g (58 mmole) 7-(4′-tert-Butyl-phenyl)-2-cyclohexyl-methyl-1H-indenewere dissolved in 340 ml toluene and 20 ml of THF in a 1000ml-roundbottom flask. 24.4 ml of n-butyl lithium (2.6 M in toluene, 63.4mmole, 1.1 eq.) were added at room temperature and the solution wasstirred for 1 h at 80° C. After cooling to 40° C. 3.5 ml (3.74 g, 29mmole, 0.5 eq.) dimethyldichlorosilane were added in one portion and themixture was stirred at 60° C. for 8.5 h. The solvent mixture was removedin vacuo (purity of the ligand >99% according to GC-analysis) and theligand was dissolved in 200 ml of diethyl ether (yellowish suspensiondue to LiCl). 23.8 ml of n-butyl lithium (61.9 mmole, 1.07 eq. regardingto “indene”, 2.6 M in toluene) were added at room temperature and themixture was stirred overnight at room temperature. Then 7.1 g (30.5mmole, 0.525 eq. regarding to “indene”) zirconium tetrachloride wereadded in portions. The orange-yellow suspension was stirred for 5 h atroom temperature and the solid was isolated by filtration. Washing with2 portions of 30 ml diethyl ether each and drying in vacuo yielded 22.7g of the crude complex (rac/meso=1.5:1, containing lithium chloride).The racemic complex was isolated by fractional crystallization fromtoluene. Yield: 8.1 g (9 mmol, 31%) as a bright yellow powder. ¹H-NMR(400 MHz, CDCl₃): δ=7.61 (d, 2H, aromatic), 7.57, 7.44 (2×d, 8H,aromatic), 7.36 (d, 2H, aromatic), 7.22, 7.15, 7.07 (3×m, 10H,aromatic+toluene), 6.94 (s, 2H, indenyl-H), 2.64 (“dd”, 2H,indenyl-CH₂), 2.34 (s, toluene) 2.13 (“dd”, 2H, indenyl-CH₂), 1.75-1.45(m, 10H, aliphatic), 1.33 (s, 18H, C(CH₃)₃), 1.31 (s, 6H, Si(CH₃)₂),1.12-0.76 (m, 12H, aliphatic) ppm.

Example 2Dimethylsilandiyl-bis-(2-(cyclohexylmethyl)-4-(1-naphthyl)-1-indenyl)-zirconiumdichloride 7-(1-Naphthyl)-2-cyclohexylmethyl-indan-1-one

18.5 g (70.4 mmole) 7-Chloro-2-cyclohexylmethyl-indan-1-one, 14.5 g (1.2eq.) naphthyl boronic acid, 16.4 g sodium carbonate, 230 ml ethyleneglycol and 45 ml water were placed in a 1 l-roundbottom flask equippedwith a mechanical stirrer and a reflux condenser. The mixture wasdegassed three times by slight evacuation and recharging with argon. Apremixed catalyst solution consisting of 32 mg (0.2 mole %) palladiumacetate, 0.94 ml NaTPPTS (2.6 M in water, 0.8 mole %) and 3 ml of waterwas added and the mixture was refluxed at 125° C. until completeconversion (approx. 5 h). 100 ml of water were added and the mixture wasextracted three times with 100 ml of toluene each. The combined organiclayers were washed twice with 100 ml water and once with 100 ml of asaturated sodium chloride solution. Drying over magnesium sulphate andevaporation of the solvent in vacuo yielded 24 g (96%) of the desiredproduct as a yellow sticky oil. ¹H-NMR (400 MHz, CDCl₃): δ=7.86 (d, 2 h,aromatic), 7.63 (m, 1H, aromatic), 7.52 (m, 2H, aromatic), 7.43 (m, 2H,aromatic), 7.33 (m, 3H, aromatic), 2.39 (m, 1H, (C═O)CH), 2.85, 2.67(2×m, 2H, benzylic), 1.90-0.80 (m, 13H, aliphatic) ppm.

7-(1-Naphthyl)-2-cyclohexylmethyl-1H-indene

24 g (68 mmole) 7-(1-Naphthyl)-2-cyclohexylmethyl-indan-1-one weredissolved in 85 ml toluene in a 500 ml-roundbottom flask equipped with areflux condenser. 2.82 g (1.1 eq.) sodium borohydride were added. Then11.8 ml (4.3 eq.) methanol were added at 50° C. and the mixture wasstirred for 5 h at 50° C. 2M sulphuric acid was added until the gasevolution ceased. After addition of 100 ml water the layers wereseparated and the organic layer was washed two times with 2M sulphuricacid and once with a saturated sodium chloride solution. The solvent wasevaporated and the crude indanol was dissolved in approx. 250 ml oftoluene. After addition of 0.5 g p-toluene sulfonic acid the mixture washeated to reflux using a Dean-Stark-trap until TLC showed completeconversion (90 min). The solution was washed twice with a saturatedNaHCO₃-solution, once with water and once with a saturated sodiumchloride solution. Drying over magnesium sulphate and evaporation of thesolvent afforded 21.65 g (95%) of the desired indene as a slightlyoffwhite oil. ¹H-NMR (400 MHz, CDCl₃): δ=7.88 (m, 2H, aromatic), 7.73(d, 1H, aromatic), 7.55-7.19 (m, 7H, aromatic), 6.10 (s, 1H, C═CH), 3.40(s, 2H, benzylic) 2.25 (d, 2H CH₂Cy), 1.67-0.80 (m, 11H, aliphatic) ppm.

Dimethylsilandiyl-bis-(2-(cyclohexylmethyl)-4-(1-naphthyl)-1-indenyl)-zirconiumdichloride

10 g (30 mmole) 7-(1-naphthyl)-2-cyclohexyl-methyl-1H-indene weredissolved in 170 ml toluene and 10 ml of THF in a 500 ml-roundbottomflask. 12.4 ml of n-butyl lithium (2.6 M in toluene, 31 mmole, 1.05 eq.)were added at room temperature and the solution was stirred for 1 h at80° C. After cooling to 40° C. 1.91 g (15 mmole, 0.5 eq.)dimethyldichlorosilane were added in one portion and the mixture wasstirred at 60° C. for 22 h. The solvent mixture was removed in vacuo andthe ligand was dissolved in 100 ml of diethyl ether. 12.4 ml of n-butyllithium (2.6 M in toluene, 31 mmole, 1.05 eq.) were added at roomtemperature and the mixture was stirred overnight at room temperature.Then 3.65 g (15.6 mmole, 0.52 eq. regarding to “indene”) zirconiumtetrachloride were added in portions. The orange-yellow suspension wasstirred for 6 h at room temperature and the solid was isolated byfiltration. Washing with 2 portions of 30 ml diethyl ether each anddrying in vacuo yielded 11.3 g of the crude complex (rac/meso=1.7:1,containing lithium chloride). The racemic complex was isolated byfractional crystallization from toluene. Yield: 2.77 g (3 mmole, 21%) asa bright orange powder. ¹H-NMR (400 MHz, CDCl₃): δ=7.85 (m, 4H,aromatic), 7.71 (m, 4H, aromatic), 7.51 (m, 4H, aromatic), 7.43-7.10(4×m, 8H, aromatic), 6.40 (s, 2H, indenyl-CH), 2.67, 2.03 (2×m, 4H,CH₂Cy), 1.65-0.68 (m, 28H, aliphatic+Si(CH₃)₂) ppm.

Example 3Dimethylsilandiyl-bis-(2-(cyclohexylmethyl)-4-(4′-methylphenyl)-1-indenyl)-zirconiumdichloride 7-(4′-Methylphenyl)-2-cyclohexylmethyl-indan-1-one

24.16 g (91.9 mmole) 7-Chloro-2-cyclohexylmethyl-indan-1-one, 15.0 g(1.2 eq.) 4-methylphenyl boronic acid, 19.49 g sodium carbonate, 303 mlethylene glycol and 57 ml water were placed in a 1 l-roundbottom flaskequipped with a mechanical stirrer and a reflux condenser. The mixturewas degassed three times by slight evacuation and recharging with argon.A premixed catalyst solution consisting of 41 mg (0.2 mole %) palladiumacetate, 1.2 ml NaTPPTS (2.6 M in water, 0.8 mole %) and 2 ml of waterwas added and the mixture was refluxed at 125° C. until completeconversion (approx. 8 h). 100 ml of water were added and the mixture wasextracted three times with 100 ml of toluene each. The combined organiclayers were washed twice with 100 ml water and once with 100 ml of asaturated sodium chloride solution. Drying over magnesium sulphate andevaporation of the solvent in vacuo yielded 30.57 g (quant.) of thedesired product as a yellow sticky oil. ¹H-NMR (400 MHz, CDCl₃):δ=7.60-7.19 (m, 7H, aromatic), 3.31 (m, 1H, (C═O)CH), 2.91-2.61 (m, 2H,benzylic), 2.38 (s, 3H, Ph-CH₃), 1.80-0.85 (m, 10H, aliphatic) ppm.

7-(4′-Methylphenyl)-2-cyclohexylmethyl-1H-indene

30.5 g (95.7 mmole) 7-(4′-Methylphenyl)-2-cyclohexylmethyl-indan-1-onewere dissolved in 89 ml toluene in a 500 ml-roundbottom flask equippedwith a reflux condenser. 3.62 g (1.0 eq.) sodium borohydride were added.Then 17.9 ml (4.35 eq.) methanol were added at 50° C. and the mixturewas stirred for 8 h at 50° C. 2M sulphuric acid was added until the gasevolution ceased. After addition of 100 ml water the layers wereseparated and the organic layer was washed two times with 2M sulphuricacid and once with a saturated sodium chloride solution. The solvent wasevaporated and the crude indanol was dissolved in approx. 200 ml oftoluene. After addition of 0.4 g p-toluene sulfonic acid the mixture washeated to reflux using a Dean-Stark-trap until TLC showed completeconversion (90 min). The solution was washed twice with a saturatedNaHCO₃-solution, once with water and once with a saturated sodiumchloride solution. Drying over magnesium sulphate and evaporation of thesolvent afforded 29 g (quant.) of the desired indene as a slightlyoffwhite oil. ¹H-NMR (400 MHz, CDCl₃): δ=7.42-7.14 (m, 7H, aromatic),6.66 (s, 1H, C═CH), 3.36 (s, 2H, benzylic), 2.41 (s, 3H, PhCH₃), 2.35(d, 2H, CH₂Cy), 1.70-0.83 (m, 11H, aliphatic) ppm.

Dimethylsilandiyl-bis-(2-(cyclohexylmethyl)-4-(4′-methylphenyl)-1-indenyl)-zirconiumdichloride

5 g (16.5 mmole) 7-(4′-Methylphenyl)-2-cyclohexyl-methyl-1H-indene weredissolved in 97 ml toluene and 5.7 ml of THF in a 250 ml-roundbottomflask. 6.9 ml of n-butyl lithium (2.5 M in toluene, 17.4 mmole, 1.05eq.) were added at room temperature and the solution was stirred for 1 hat 80° C. After cooling to 40° C. 1.0 ml (8.3 mmole, 0.5 eq.)dimethyldichlorosilane were added in one portion and the mixture wasstirred at 60° C. for 6 h. The solvent mixture was removed in vacuo andthe ligand was dissolved in 55 ml of diethyl ether. 6.6 ml of n-butyllithium (2.5 M in toluene, 16.5 mmole, 1.0 eq.) were added at roomtemperature and the mixture was stirred overnight at room temperature.Then 1.93 g (8.3 mmole, 0.5 eq. regarding to “indene”) zirconiumtetrachloride were added in portions. The orange-yellow suspension wasstirred for 3 h at room temperature and the solid was isolated byfiltration. Washing with 2 portions of 30 ml diethyl ether each anddrying in vacuo yielded 4.24 g of the crude complex (rac/meso=1.8:1,containing lithium chloride). The racemic complex was isolated byfractional crystallization from toluene. Yield: 0.76 g (0.9 mmole, 11%)as a bright yellow powder. ¹H-NMR (400 MHz, CDCl₃): δ=7.61 (d, 2H,aromatic), 7.52 (d, 4H, aromatic), 7.35 (d, 2H, aromatic), 7.27-7.06 (m,6H, aromatic), 6.89 (s, 2H, indenyl-CH), 2.64, 2.11 (2×m, 4H, CH₂Cy),2.36 (s, 6H, PhCH₃), 1.66-0.73 (m, 28H, aliphatic+Si(CH₃)₂) ppm.

Example 4Dimethylsilandiyl-bis-(2-(cyclohexylmethyl)-4-(3′,5′-dimethylphenyl)-1-indenyl)-zirconiumdichloride 7-(3′,5′-Dimethylphenyl)-2-cyclohexylmethyl-indan-1-one

20 g (76 mmole) 7-Chloro-2-cyclohexylmethyl-indan-1-one, 13.7 g (1.2eq.) 2,3-dimethylphenyl boronic acid, 17.75 g sodium carbonate, 250 mlethylene glycol and 50 ml water were placed in a 1 l-roundbottom flaskequipped with a mechanical stirrer and a reflux condenser. The mixturewas degassed three times by slight evacuation and recharging with argon.A premixed catalyst solution consisting of 34 mg (0.2 mole %) palladiumacetate, 1 ml NaTPPTS (2.6 M in water, 0.8 mole %) and 2 ml of water wasadded and the mixture was refluxed at 125° C. until complete conversion(approx. 4 h). 100 ml of water were added and the mixture was extractedthree times with 100 ml of toluene each. The combined organic layerswere washed twice with 100 ml water and once with 100 ml of a saturatedsodium chloride solution. Drying over magnesium sulphate and evaporationof the solvent in vacuo yielded 27.7 g (quant.) of the desired productas a yellow sticky oil. ¹H-NMR (400 MHz, CDCl₃): δ=7.55 (t, 1H,aromatic), 7.39 (d, 1H, aromatic), 7.28-7.02 (m, 3H, aromatic), 3.34 (m,1H, (C═O)CH), 2.81-2.69 (m, 2H, benzylic), 2.37 (s, 6H, Ph-CH₃),1.89-0.89 (m, 10H, aliphatic) ppm.

7-(3′,5′-Dimethylphenyl)-2-cyclohexylmethyl-1H-indene

25.3 g (76.1 mmole)7-(3′,5′-Dimethylphenyl)-2-cyclohexyl-methyl-indan-1-one were dissolvedin 90 ml toluene in a 500 ml-roundbottom flask equipped with a refluxcondenser. 3.17 g (1.1 eq.) sodium borohydride were added. Then 13.3 ml(4.35 eq.) methanol were added at 50° C. and the mixture was stirred for3 h at 50° C. 2M sulphuric acid was added until the gas evolutionceased. After addition of 100 ml water the layers were separated and theorganic layer was washed two times with 2M sulphuric acid and once witha saturated sodium chloride solution. The solvent was evaporated and thecrude indanol was dissolved in approx. 90 ml of toluene. After additionof 0.3 g p-toluene sulfonic acid the mixture was heated to reflux usinga Dean-Stark-trap until TLC showed complete conversion (90 min). Thesolution was washed twice with a saturated NaHCO₃-solution, once withwater and once with a saturated sodium chloride solution. Drying overmagnesium sulphate and evaporation of the solvent afforded 22.1 g (92%)of the desired indene as a slightly offwhite oil. ¹H-NMR (400 MHz,CDCl₃): δ=7.35 (d, 1H, aromatic), 7.24 (m, 1H, aromatic), 7.15 (m, 3H,aromatic), 7.01 (s, 1H, aromatic), 6.68 (s, 1H, C═CH), 3.37 (s, 2H,benzylic), 2.39 (s, 6H, PhCH₃), 2.36 (d, 2H, CH₂Cy), 1.74-0.91 (m, 11H,aliphatic) ppm.

Dimethylsilandiyl-bis-(2-(cyclohexylmethyl)-4-(3′,5′-dimethylphenyl)-1-indenyl)-zirconiumdichloride

2 g (6.32 mmole) 7-(3′,5′-Dimethylphenyl)-2-cyclo-hexylmethyl-1H-indenewere dissolved in 34 ml toluene and 2 ml of THF in a 100 ml-roundbottomflask. 2.65 ml of n-butyl lithium (2.5 M in toluene, 6.63 mmole, 1.05eq.) were added at room temperature and the solution was stirred for 1 hat 80° C. After cooling to 40° C. 408 mg (3.2 mmole, 0.5 eq.)dimethyldichlorosilane were added in one portion and the mixture wasstirred at 60° C. for 18 h. After cooling to room temperature 2.65 ml ofn-butyl lithium (2.5 M in toluene, 6.63 mmole, 1.05 eq.) were added atroom temperature and the mixture was stirred for 1 h at 80° C. Aftercooling to room temperature 781 mg (3.35 mmole, 0.53 eq. regarding to“indene”) zirconium tetrachloride were added in portions. Theorange-yellow suspension was stirred for 20 h at room temperature andthe LiCl was removed by filtration over celite. The celite pad waswashed once with 20 ml of toluene and the solvent was removed in vacuo.The racemic complex was isolated by fractional crystallization fromtoluene, followed by washing with diethyl ether. Yield: 0.20 g (0.24mmole, 7.5%) as a bright yellow powder. ¹H-NMR (400 MHz, CDCl₃): δ=7.59(d, 2H, aromatic), 7.35 (d, 2H, aromatic), 7.28-6.92 (m, 8H, aromatic),6.78 (s, 2H, indenyl-CH), 2.65, 2.15 (2×m, 4H, CH₂Cy), 2.38 (s, 12H,PhCH₃), 1.64-0.86 (m, 28H, aliphatic+Si(CH₃)₂) ppm.

Example 5Dimethylsilandiyl-bis-(2-(tert-butylmethyl)-4-(4′-tert-butylphenyl)-1-indenyl)-zirconiumdichloride 1-Bromo-3,3-dimethyl-butane

In a 1 l-roundbottom flask equipped with a reflux condenser 232 gconcentrated sulphuric acid and 283 g hydrobromic acid (48% in water)were added successively under cooling with an ice bath to 100 g (0.98mole) 3,3-dimethyl-1-butanol. The mixture was refluxed for 6 h and aftercooling to room temperature given to 400 g of ice. The aqueous phase wasextracted with 400 ml pentane. The organic layer was washed with a 2 MNaOH-solution and with water, dried over magnesium sulphate, and thesolvent was removed in vacuo. The product was distilled in vacuo toyield 88.1 g (55%) of 1-bromo-3,3-dimethyl-butane as a colourless oil.¹H-NMR (400 MHz, CDCl₃): δ=3.35 (m, 2H, CH₂Br), 1.80 (m, 2H, CH₂), 0.90(s, 9H, t-Bu) ppm.

1-(2-Chloro-phenyl)-4,4-dimethyl-pentan-1-one

14.1 g (580 mmole) Magnesium turnings were placed in a 1 l-roundbottomflask equipped with a dropping funnel and a reflux condenser, and 60 mlof THF were added. The magnesium was etched slightly with a few crystalsof iodine and then 2 g of 1-bromo-3,3-dimethyl-butane were added and themixture was heated locally. After the start of the Grignard-formationthe rest of the 1-bromo-3,3-dimethyl-butane in 350 ml of THF (88.1 g intotal, 533 mmole) were added within a period of 20 min. The mixture wasrefluxed for 1.5 h and then cooled to room temperature. In a separate 2l-roundbottom flask 63.9 g (464 mmole) of 2-chloro-benzonitrile and 141mg (0.16 mole %) copper(I)iodide were dissolved in 265 ml of THF. TheGrignard-solution was added dropwise over a period of 30 min and thereaction mixture was refluxed for 3 h. After standing overnight at roomtemperature, a mixture of 190 ml water and 127 ml concentratedhydrochloric acid were added very carefully, causing a stronglyexothermic reaction. The mixture was stirred at 50° C. for 1 h and thelayers were separated. The aqueous layer was extracted twice with 150 mlof toluene each. The combined organic layers were washed twice with 2 Msulphuric acid, once with a saturated sodium bicarbonate solution andonce with a saturated sodium chloride solution. After drying overmagnesium sulphate the solvent was evaporated in vacuo to yield 103.8 g(quant.) of the desired phenone as slightly brown oil. ¹H-NMR (400 MHz,CDCl₃): δ=7.41-7.26 (m, 4H, aromatic), 2.87 (m, 2H, COCH₂), 1.59 (m, 2H,CH₂-t-Bu), 0.90 (s, 9H, t-Bu) ppm.

7-Chloro-2-(2,2-dimethyl-propyl)-indan-1-one

101.8 g (453 mmole) 1-(2-Chloro-phenyl)-4,4-dimethyl-pentan-1-one, 133.4g (2.1 eq.) urotropine and 124.7 g (2.7 eq.) of acetic anhydride wereplaced in a 1000 ml roundbottom flask and the mixture was stirred at 80°C. for 4 h. Then 200 ml water and 200 ml 2M NaOH were added and themixture was extracted two times with 250 ml dichloromethane each. Theorganic layer was washed two times with 150 ml saturated aqueousammonium chloride and dried over magnesium sulphate. The solvent amountwas reduced in vacuo to a total of 250 ml volume and the solution wasadded dropwise over a period of 2.5 h to 1000 g of hot (70-75° C.)concentrated sulphuric acid. After stirring for an additional 30 min at75° C. the mixture was allowed to stand overnight at room temperature.The mixture was given to approx. 800 g of ice and extracted three timeswith 250 ml dichloromethane each. The organic layer was washed twicewith 250 ml of a saturated sodium bicarbonate solution and once with 200ml of a saturated sodium chloride solution. After drying over magnesiumsulphate the solvent was removed in vacuo. The product was purified bycolumn chromatography on silica (heptane/dichloromethane 1:1) to yield79.4 g (74%) of the desired product as a slightly off-white oil, whichslowly crystallized. ¹H-NMR (400 MHz, CDCl₃): δ=7.44 (t, 1H, aromatic),7.30 (d, 1H, aromatic), 7.27 (d, 1H, aromatic), 3.38 (dd, 1H, COCH),2.79, 2.60 (2×m, 2H, benzylic), 2.10, 1.21 (2×m, 1H, CH₂-t-Bu), 0.90 (s,9H, t-Bu) ppm.

7-(4′-tert-Butyl-phenyl)-2-(2,2-dimethyl-propyl)-indan-1-one

35 g (148 mmole) 7-Chloro-2-(2,2-dimethyl-propyl)-indan-1-one, 31.6 g(1.2 eq.) tert-butylphenyl boronic acid, 34.5 g sodium carbonate, 438 mlethylene glycol and 88 ml water were placed in a 1 l-roundbottom flaskequipped with a mechanical stirrer and a reflux condenser. The mixturewas degassed three times by slight evacuation and recharging with argon.A premixed catalyst solution consisting of 67 mg (0.2 mole %) palladiumacetate, 1.94 ml NaTPPTS (2.6 M in water, 0.8 mole %) and 2 ml of waterwas added and the mixture was refluxed at 125° C. until completeconversion (approx. 4 h). 100 ml of water were added and the mixture wasextracted three times with 100 ml of toluene each. The combined organiclayers were washed twice with 100 ml water and once with 100 ml of asaturated sodium chloride solution. Drying over magnesium sulphate andevaporation of the solvent in vacuo yielded 58.82 g (quant.) of thedesired product as a yellow sticky oil. ¹H-NMR (400 MHz, CDCl₃): δ=7.58(t, 1H, aromatic), 7.48-7.17 (m, 6H, aromatic), 3.48 (m, 1H, (C═O)CH),2.88, 2.63 (2×m, 2H, benzylic), 2.38 (s, 1H), 2.13 (m, 1H, CH₂-t-Bu),1.40 (s, 9H, Ph-t-Bu), 1.03 (s, 9H, CH₂-t-Bu) ppm.

4-(4′-tert-Butyl-phenyl)-2-(2,2-dimethyl-propyl)-1H-indene

50 g (150 mmole)7-(4′-tert-Butyl-phenyl)-2-(2,2-dimethyl-propyl)-indan-1-one weredissolved in 180 ml toluene in a 500 ml-roundbottom flask equipped witha reflux condenser. 6.22 g (1.1 eq.) sodium borohydride were added. Then26.1 ml (4.3 eq.) methanol were added at 50° C. and the mixture wasstirred for 4 h at 50° C. Another 3.11 g sodium borohydride and 10.3 gmethanol were added and the mixture was stirred at 50° C. overnight. 2Msulphuric acid was added until the gas evolution ceased. After additionof 100 ml water the layers were separated and the organic layer waswashed two times with 2M sulphuric acid and once with a saturated sodiumchloride solution. The solvent was evaporated and the crude indanol wasdissolved in approx. 300 ml of toluene. After addition of 1 g p-toluenesulfonic acid the mixture was heated to reflux using a Dean-Stark-trapuntil TLC showed complete conversion (90 min). The solution was washedtwice with a saturated NaHCO₃-solution, once with water and once with asaturated sodium chloride solution. Drying over magnesium sulphate,evaporation of the solvent and recrystallization from 500 ml ethanolafforded 35.3 g (74%) of the desired indene as white crystals. ¹H-NMR(400 MHz, CDCl₃): δ=7.47 (s, 4H, aromatic), 7.34 (d, 1H, aromatic), 7.25(d, 1H, aromatic), 7.16 (t, 1H, aromatic), 6.72 (s, 1H, C═CH), 3.44 (s,2H, benzylic), 2.36 (s, 2H, CH₂-t-Bu), 1.37 (s, 9H, Ph-t-Bu), 0.96 (s,9H, CH₂-t-Bu) ppm.

Dimethylsilandiyl-bis-(2-(tert-butylmethyl)-4-(4′-tert-butylphenyl)-1-indenyl)zirconiumdichloride

2 g (6.28 mmole)4-(4-tert-Butyl-phenyl)-2-(2,2-dimethyl-propyl)-1H-indene were dissolvedin 34 ml toluene and 2 ml of THF in a 100 ml-roundbottom flask. 2.64 mlof n-butyl lithium (2.5 M in toluene, 6.6 mmole, 1.05 eq.) were added atroom temperature and the solution was stirred for 1 h at 80° C. Aftercooling to 40° C. 405 mg (3.2 mmole, 0.5 eq.) dimethyldichlorosilanewere added in one portion and the mixture was stirred at 60° C. for 17h. The solvent was removed in vacuo and 20 ml diethyl ether were added.2.64 ml of n-butyl lithium (2.5 M in toluene, 6.6 mmole, 1.05 eq.) wereadded at room temperature and the mixture was stirred overnight at roomtemperature. After cooling to room temperature 776 mg (3.3 mmole, 0.53eq. regarding to “indene”) zirconium tetrachloride were added inportions. The orange-yellow suspension was stirred for 5 h at roomtemperature and the complex was isolated by filtration and washing withdiethyl ether to yield 1.59 g crude complex. The racemic form wasisolated by fractional recrystallization from toluene. Yield: 0.65 g(24%) as a bright yellow powder. ¹H-NMR (400 MHz, CDCl₃): δ=7.62 (d, 2H,aromatic), 7.58, 7.45 (2×d, 8H, aromatic), 7.37 (d, 2H, aromatic), 7.23,7.16, 7.08 (3×m, 10H, aromatic+toluene), 6.93 (s, 2H, indenyl-H), 2.64(d, 2H, indenyl-CH₂), 2.34 (s, toluene), 2.15 (d, 2H, indenyl-CH₂), 1.35(s, 6H, Si(CH₃)₂), 1.32 (s, 18H, Ph-t-Bu), 0.83 (s, 18H, CH₂-t-Bu) ppm.

Example 6Dimethylsilandiyl-bis-(2-(1-adamantylmethyl)-4-(4′-tert-butylphenyl)-1-indenyl)zirconiumdichloride 1-(2-Bromo-ethyl)-adamantine

In a 1 l-roundbottom flask equipped with a reflux condenser 164 gconcentrated sulphuric acid and 200 g hydrobromic acid (48% in water)were added subsequently under cooling with an ice bath to 126.20 g (0.70mole) 2-(1-adamantyl)ethanol. The mixture was refluxed for 6 h and aftercooling to room temperature given to 400 g of ice. The aqueous phase wasextracted with 400 ml pentane. The organic layer was washed with a 2 MNaOH-solution and with water, dried over magnesium sulphate, and thesolvent was removed in vacuo. The product was distilled in vacuo toyield 153.2 g (90%) of (1-(2-Bromo-ethyl)-adamantane as a colourlessoil. ¹H-NMR (400 MHz, CDCl₃): δ=3.29 (t, 2H, CH₂Br), 1.71 (t, 2H,CCH₂CH₂Br), 1.56-1.17 (m, 15H, aliphatic) ppm.

1-(2-Chloro-phenyl)-3-(1-adamantyl)-propan-1-one

15.57 g (640 mmole) Magnesium turnings were placed in a 1 l-roundbottomflask equipped with a dropping funnel and a reflux condenser, and 50 mlof THF were added. The magnesium was etched slightly with a few crystalsof iodine and then 2 g of (1-(2-bromo-ethyl)-adamantane were added andthe mixture was heated locally. After the start of theGrignard-formation the rest of the (1-(2-bromo-ethyl)-adamantane in 350ml of THF (143.5 g in total, 590 mmole) were added within a period of 20min. The mixture was refluxed for 1.5 h and then cooled to roomtemperature. In a separate 2 l-roundbottom flask 70.5 g (513 mmole) of2-chloro-benzonitrile and 156 mg (0.16 mole %) copper(I)iodide weredissolved in 130 ml of THF. The Grignard-solution was added dropwiseover a period of 30 min and the reaction mixture was refluxed for 3 h.After standing overnight at room temperature, a mixture of 190 ml waterand 127 ml concentrated hydrochloric acid were added very carefully,causing a strongly exothermic reaction. The mixture was stirred at 50°C. for 1 h and the layers were separated. The aqueous layer wasextracted twice with 150 ml of toluene each. The combined organic layerswere washed twice with 2 M sulphuric acid, once with a saturated sodiumbicarbonate solution and once with a saturated sodium chloride solution.After drying over magnesium sulphate the solvent was evaporated in vacuoto yield 178.7 g (quant.) of the desired phenone as slightly brown oil.¹H-NMR (400 MHz, CDCl₃): δ=7.39-7.12 (m, 4H, aromatic), 2.55 (t, 2H,COCH₂), 1.40-1.13 (m, 17H, aliphatic) ppm.

7-Chloro-2-(1-adamantylmethyl)-indan-1-one

78.7 g (260 mmole) 1-(2-Chloro-phenyl)-3-(1-adamantyl)-propan-1-one,77.5 g (2.1 eq.) urotropine and 72.6 g (2.7 eq.) of acetic anhydridewere placed in a 500 ml roundbottom flask and the mixture was stirred at80° C. for 4 h. Then 100 ml water and 100 ml 2M NaOH were added and themixture was extracted two times with 200 ml dichloromethane each. Theorganic layer was washed two times with 100 ml saturated aqueousammonium chloride and dried over magnesium sulphate. The solvent amountwas reduced in vacuo to a total of 150 ml volume and the solution wasadded dropwise over a period of 2.5 h to 660 g of hot (70-75° C.)concentrated sulphuric acid. After stirring for an additional 30 min at75° C. the mixture was allowed to stand overnight at room temperature.The mixture was given to approx. 500 g of ice and extracted three timeswith 150 ml dichloromethane each. The organic layer was washed twicewith 150 ml of a saturated sodium bicarbonate solution and once with 100ml of a saturated sodium chloride solution. After drying over magnesiumsulphate the solvent was removed in vacuo. The product was purified bycolumn chromatography on silica (heptane/dichloromethane 5:1) to yield58 g (71%) of the desired product as a slightly off-white glassy solid.¹H-NMR (400 MHz, CDCl₃): δ=7.39 (t, 1H, aromatic), 7.27 (d, 1H,aromatic), 7.21 (d, 1H, aromatic), 3.37 (dd, 1H, COCH), 2.70 (m, 2H,benzylic), 1.36-1.18 (m, 17H, aliphatic) ppm.

7-(4′-tert-Butyl-phenyl)-2-(1-adamantylmethyl)-indan-1-one

71.8 g (228 mmole) 7-Chloro-2-(1-adamantylmethyl)-indan-1-one, 49 g (1.2eq.) 4-tert-butyl-benzene boronic acid, 53 g sodium carbonate, 750 mlethylene glycol and 150 ml water were placed in a 2 l-roundbottom flaskequipped with a mechanical stirrer and a reflux condenser. The mixturewas degassed three times by slight evacuation and recharging with argon.A premixed catalyst solution consisting of 103 mg (0.2 mole %) palladiumacetate, 3 ml NaTPPTS (2.6 M in water, 0.8 mole %) and 2 ml of water wasadded and the mixture was refluxed at 125° C. until complete conversion(approx. 6 h). 300 ml of water were added and the mixture was extractedthree times with 150 ml of toluene each. The combined organic layerswere washed twice with 100 ml water and once with 100 ml of a saturatedsodium chloride solution. Drying over magnesium sulphate and evaporationof the solvent in vacuo yielded 94.1 g (quant.) of the desired productas a yellow sticky oil. ¹H-NMR (400 MHz, CDCl₃): δ=7.52 (t, 1H,aromatic), 7.41, 7.36 (2×d, 4H, aromatic), 7.21 (m, 2H, aromatic), 3.37(m, 1H, COCH), 2.77-2.68 (m, 2H, benzylic), 1.42-1.18 (m, 26H, aliphatic& C(CH₃)₃) ppm.

7-(4′-tert-Butyl-phenyl)-2-(1-adamantylmethyl)-1H-indene

94.0 g (228 mmole)7-(4′-tert-Butyl-phenyl)-2-(1-adamantylmethyl)-indan-1-one weredissolved in 291 ml toluene in a 1 l-roundbottom flask equipped with areflux condenser. 9.5 g (1.1 eq.) sodium borohydride were added. Then 40ml (4.3 eq.) methanol were added at 50° C. and the mixture was stirredfor 6 h at 50° C. 2M sulphuric acid was added until the gas evolutionceased. After addition of 100 ml water the layers were separated and theorganic layer was washed two times with 2M sulphuric acid and once witha saturated sodium chloride solution. The solvent was evaporated and thecrude indanol was dissolved in approx. 350 ml of toluene. After additionof 0.7 g p-toluene sulfonic acid the mixture was heated to reflux usinga Dean-Stark-trap until TLC showed complete conversion (90 min). Thesolution was washed twice with a saturated NaHCO₃-solution, once withwater and once with a saturated sodium chloride solution. Drying overmagnesium sulphate, evaporation of the solvent and crystallization from900 ml ethanol afforded 76.9 g (85%) of the desired indene as whitecrystals. ¹H-NMR (400 MHz, CDCl₃): δ=7.44, 7.32, 7.23, 7.12 (4×m, 7H,aromatic), 6.63 (s, 1H, ═CH), 3.32 (s, 2H, benzylic), 2.29 (d, 2H,aliphatic), 1.69-1.15 (m, 15H, aliphatic), 1.38 (s, 9H, C(CH₃)₃) ppm.

Dimethylsilandiyl-bis-(2-(1-adamantylmethyl)-4-(4′-tert-butylphenyl)-1-indenyl)-zirconiumdichloride

23 g (58 mmole) 7-(4′-tert-Butyl-phenyl)-2-(1-adamantylmethyl)-1H-indenewere dissolved in 340 ml toluene and 20 ml of THF in a 1000ml-roundbottom flask. 24.4 ml of n-butyl lithium (2.6 M in toluene, 63.4mmole, 1.1 eq.) were added at room temperature and the solution wasstirred for 1 h at 80° C. After cooling to 40° C. 3.5 ml (3.74 g, 29mmole, 0.5 eq.) dimethyldichlorosilane were added in one portion and themixture was stirred at 60° C. for 8.5 h. The solvent mixture was removedin vacuo (purity of the ligand >94% according to GC-analysis) and theligand was dissolved in 200 ml of diethyl ether (yellowish suspensiondue to LiCl). 23.8 ml of n-butyl lithium (61.9 mmole, 1.07 eq. regardingto “indene”, 2.6 M in toluene) were added at room temperature and themixture was stirred overnight at room temperature. Then 7.1 g (30.5mmole, 0.525 eq. regarding to “indene”) zirconium tetrachloride wereadded in portions. The orange-yellow suspension was stirred overnight atroom temperature and the solid was isolated by filtration. Washing with2 portions of 35 ml diethyl ether each and drying in vacuo yielded 25.1g of the crude complex (rac/meso=1.6:1, containing lithium chloride).The racemic complex was isolated by fractional crystallization fromtoluene. Yield: 9.8 g (9.7 mmol, 33%) as a bright yellow powder. ¹H-NMR(400 MHz, CDCl₃): δ=7.62 (d, 2H, aromatic), 7.55, 7.42 (2×d, 8H,aromatic), 7.32 (d, 2H, aromatic), 7.21, 7.15, 7.08 (3×m, 10H,aromatic+toluene), 6.83 (s, 2H, indenyl-H), 2.53 (“dd”, 2H,indenyl-CH₂), 2.34 (s, toluene) 2.09 (“dd”, 2H, indenyl-CH₂), 1.75-1.15(m, 30H, aliphatic), 1.34 (s, 18H, C(CH₃)₃), 1.32 (s, 6H, Si(CH₃)₂) ppm.

Example 7(Methyl)(n-propyl)silandiyl-bis-(2-(cyclohexylmethyl)-4-(4′-tert-butylphenyl)-1-indenyl)-zirconiumdichloride

2.0 g (5.8 mmole) 7-(4′-tert-Butyl-phenyl)-2-cyclohexyl-methyl-1H-indenewere dissolved in 10 ml dimethoxy ethane in a 100 ml-roundbottom flask.2.44 ml of n-butyl lithium (2.6 M in toluene, 6.34 mmole, 1.1 eq.) wereadded at room temperature and the solution was stirred for 1 h at 80° C.After cooling to 40° C. 456 mg (2.9 mmole, 0.5 eq.)(methyl)(n-propyl)dichlorosilane were added in one portion and themixture was stirred at 60° C. for 17 h. The solvent mixture was removedin vacuo (purity of the ligand >99% according to GC-analysis) and theligand was dissolved in 20 ml of diethyl ether (yellowish suspension dueto LiCl). 2.44 ml of n-butyl lithium (6.34 mmole, 1.05 eq. regarding to“indene”, 2.6 M in toluene) were added at room temperature and themixture was stirred overnight at room temperature. Then 718 mg (3.08mmole, 0.53 eq. regarding to “indene”) zirconium tetrachloride wereadded in portions. The orange-yellow suspension was stirred for 5 h atroom temperature and the lithium chloride was removed by filtration andwashing two times with 5 ml of diethyl ether each. The solvent wasremoved in vacuo and the residue was recrystallized from heptane toyield 660 mg (0.707 mmole, 24%) of the racemic complex as a brightyellow powder. ¹H-NMR (400 MHz, CDCl₃): δ=7.62 (d, 2H, aromatic), 7.57,7.44 (2×d, 8H, aromatic), 7.35 (d, 2H, aromatic), 7.11-7.06 (m, 2H,aromatic), 6.94 (s, 2H, indenyl-H), 2.63 (“dd”, 2H, indenyl-CH₂), 2.13(“dd”, 2H, indenyl-CH₂), 1.88 (m, 4H, aliphatic), 1.67-1.45 (m, 12Haliphatic), 1.35 (s, 18H, C(CH₃)₃), 1.32 (s, 3H, SiCH₃), 1.31-0.76 (m,14H, aliphatic) ppm.

Comparative Example 8 Dimethylsilanediylbis(2-methylindenyl)zirconiumdichloride Preparation of Dimethylbis(2-methylindenyl)silane

8.0 g (61.4 mmoles) of 2-methylindene were introduced into 175 mL oftoluene and 13 mL of THF, and 24.6 mL of n-butyllithium (2.5 Mintoluene) were added without interruption at room temperature. After thisaddition was complete, the mixture was heated to 80° C. and stirred atthis temperature for one hour. It was allowed to cool to 40° C., then3.96 g (30.7 mmoles) of dimethyldichlorosilane were slowly addeddropwise. After this addition, the reaction solution was stirred forthree hours at 60° C. and then overnight at room temperature. 70 mL ofwater were added and the phases that form were separated. The organicphase was washed with 100 mL of water, and the aqueous phase wasextracted three times with a total of 100 mL of toluene. The combinedorganic phases were dried over magnesium sulfate. After separation ofthe magnesium sulfate, the solvent was removed and the residue waspurified by column chromatography. The desired product was isolated in ayield of 8.16 g (84%) (purity 99%).

¹H-NMR (400 MHz, CDCl₃):

7.55-7.12 (m, 8H, arom-H), 6.40 (s, br, 2H, olefin-H indene), 3.51, 3.48(each s, each 1H, SiC—H), 2.09, 2.04 (each s, each 3H, CH₃), 1.71 (s,6H, CH₃), 0.08 (s, 6H, SiMe₂).

Dimethylsilanediylbis(2-methylindenyl)zirconium dichloride

A solution of 5.0 g (15.8 mmoles) of dimethylbis(2-methylindenyl)silanein 45 mL of tetrahydrofuran was treated with 12.6 mL of ann-butyllithium solution (2.5 Min hexane) and stirred for 16 hours atroom temperature. The reaction solution was cooled to 0° C. and 1.84 g(7.9 mmoles) of zirconium tetrachloride were added in portions. Afterthis addition, the solution was heated to room temperature and stirredfor two hours at this temperature. The precipitate that forms wasfiltered through a G3 fritted glass filter, and the residue was washedonce with 10 mL of diethyl ether. The residue was then dried in avacuum, and the desired product was obtained in a yield of 1.89 g (50%)with a rac:meso ratio close to 1:1. The isomers must be separated in asubsequent step to obtain selective catalysts for propylenepolymerization.

¹H-NMR (400 MHz, CDCl₃):

7.75-6.85 (m, 10H, arom-H), 2.24 (s, 6H, CH₃), 1.25 (s, 6H, aliph-H).

Comparative Example 9Dimethylsilanediylbis(2-methyl-4,5-benzoindenyl)zirconium dichlorideDimethylbis(2-methyl-4,5-benzoindenyl)silane

A solution of 7.0 g (38.8 mmoles) of the isomeric mixture of2-methyl-4,5-benzoindene and 2-methyl-6,7-benzoindene in 65 mL oftetrahydrofuran was treated with 15.6 mL of an n-butyllithium solution(2.5 Min hexane) and heated under reflux for one hour. The resulting redsolution was then added dropwise at room temperature to a solution of2.51 g (19.4 mmoles) of dimethyldichlorosilane in 10 mL of THF, and theresulting solution was heated under reflux for 5-6 hours. The reactionsolution was then cooled to room temperature and poured into ice water.The aqueous phase was repeatedly extracted with 60 mL of diethyl ether.After the organic phase has been dried with magnesium sulfate, thesolvent was removed and the residue was purified by columnchromatography. The desired product was isolated in a yield of 4.85 g(60%).

¹H-NMR (400 MHz, CDCl₃):

8.01-7.36 (m, 12H, arom-H), 7.21 (s, br, 2H, olefin-H indene), 3.96 (s,2H, SiC—H), 2.43 (s, 6H, CH₃), −0.22 (s, 6H, SiMe₂).

Dimethylsilanediylbis(2-methyl-4,5-benzoindenyl)zirconium dichloride

A solution of 3.0 g (7.2 mmoles) ofdimethylbis(2-methyl-4,5-benzo-indenyl)silane in 30 mL oftetrahydrofuran was treated with 5.8 mL of an n-butyllithium solution(2.5 M in hexane) and stirred for 16 hours at room temperature. Thereaction solution was cooled to 0° C. and 1.68 g (7.2 mmoles) ofzirconium tetrachloride were added in portions. After this addition, thesolution was warmed to room temperature and stirred for two hours atthis temperature. The precipitate that forms was filtered through a G3flitted glass filter and the residue was washed once with 5 mL ofdiethyl ether. The residue was then dried in a vacuum, and the desiredproduct was obtained in a yield of 2.32 g (56%) with a rac:meso ratio ofabout 1:1. The isomers must be separated in a subsequent step to obtainselective catalysts for propylene polymerization.

¹H-NMR (400 MHz, CDCl₃):

7.85-7.10 (m, 14H, arom-H), 2.25 (s, 6H, CH₃), 1.30 (s, 6H, CH₃).

Comparative Example 10Dimethylsilanediylbis(2-methyl-4-(4′-tert-butylphenyl)indenyl)zirconiumdichlorideDimethylbis(2-methyl-4-(4′-tert-butylphenyl)indenyl)silane

8.0 g (30.5 mmoles) of 2-methyl-4-(4′-tert-butylphenyl)-1-indene wereintroduced into 180 mL of toluene and 10 mL of THF, then 12.4 mL ofn-butyllithium solution (2.5 M in toluene) were added withoutinterruption at room temperature. After this addition was complete, themixture was heated to 80° C. and stirred at this temperature for onehour. It was allowed to cool to 40° C., then 2.0 g (15.3 mmoles) ofdimethyldichlorosilane were slowly added dropwise. After this addition,the reaction solution was stirred for three hours at 60° C. and thenovernight at room temperature. 80 mL of water were added and the phasesthat form were separated. The organic phase was washed with 80 mL ofwater, and the aqueous phase was extracted three times with a total of80 mL of toluene. The combined organic phases were dried over magnesiumsulfate. After separation of the magnesium sulfate, the solvent wasremoved and the residue was purified by column chromatography. Thedesired product was isolated in a yield of 7.27 g (80%) (purity 97%).

¹H-NMR (400 MHz, CDCl₃):

7.73-7.12 (m, 16H, arom-H), 6.75 (s, br, 2H, olefin-H indene), 3.76 (s,2H, SiC—H), 2.17 (s, 6H, CH₃), −0.20 (m, 6H, SiMe₂).

Dimethylsilanediylbis(2-methyl-4-(4′-tert-butylphenyl)indenyl)zirconiumdichloride

143 g (0.54 moles) of 2-methyl-4-(4′-tert-butylphenyl)-1-indene wereintroduced into 2.4 L of toluene and 143 mL of tetrahydrofuran, and 234mL of an n-butyllithium solution (2.5 M in toluene) were added withoutinterruption at room temperature. After this addition was complete, themixture was heated to 80° C. and stirred for one hour at thistemperature. It was allowed to cool to 40° C., then 33.6 g (0.26 moles)of dimethyldichlorosilane were added dropwise to this reaction solution.The reaction solution was stirred for three hours at 60° C. It wascooled to room temperature, and then 218 mL of an n-butyllithiumsolution (2.5 Min toluene) were added dropwise. After this addition wascomplete, the solution was heated to 80° C. and stirred for one hour atthis temperature. It was allowed to cool to room temperature, then 71.1g (0.305 moles) of zirconium tetrachloride were added in portions. Thesolution was stirred for two hours at 45° C. and the precipitate thatforms was separated by filtration through a G3 flitted glass filter andthen carefully washed with 700 mL portions of tetrahydrofuran. Theresidue was dried in an oil-pump vacuum, and the product was obtained ina yield of 155 g (80%) and with a rac:meso ratio of 1:1. The isomersmust be separated in an additional step to obtain selective catalystsfor propylene polymerization.

¹H-NMR (400 MHz, CDCl₃):

7.63-6.85 (m, 16H, arom-H), 2.44 (s, 3H, meso-CH₃), 2.24 (s, 3H,rac-CH₃), 1.46 (s, 1.5H, meso-SiMe₂), 1.33-1.29 (m, 21H, tert-butyl,rac-SiMe₂), 1.23 (s, 1.5H, meso-CH₃).

Comparative Example 11Dimethylsilanediyl(2-methyl-4-(4′-tert-butylphenyl)indenyl)(2-isopropyl-4-(4′-tert-butylphenyl)indenyl)zirconiumdichlorideDimethylsilanediyl(2-methyl-4-(4′-tert-butylphenyl)-1-indene)(2-isopropyl-4-(4′-tert-butylphenyl)-1-indene)

16.8 g (57.7 mmoles) of 2-isopropyl-4-(4′-tert-butylphenyl)-1-indenewere introduced into 131 mL of toluene and 5.0 mL of THF, and 21.5 mL ofan n-butyllithium solution (2.68 M in toluene) were added withoutinterruption at room temperature. After this addition was complete, themixture was heated to 80° C. and stirred for one hour at thistemperature. It was then allowed to cool to room temperature. Theresulting reaction solution was added dropwise to a solution of 20.5 g(57.7 mmoles) of(2-methyl-4-(4′-tert-butylphenyl)-1-indenyl)dimethylchlorosilane in 246mL of toluene over a period of one hour. The mixture was stirredovernight at room temperature. Then 60 mL of water were added and thephases which form were separated. The organic phase was washed with 100mL of water and the combined aqueous phases were extracted twice with atotal of 100 mL of toluene. The combined organic phases were dried overmagnesium sulfate. After filtering off the magnesium sulfate, thesolvent was removed and the residue was dried in an oil pump vacuum. Thedesired product was isolated in a yield of 31.6 g (90%) (purity: 90%).

¹H-NMR (400 MHz, CDCl₃):

7.51-7.1 (m, 14H, arom-H), 6.71, 6.62 (each s, each 1H,olefin-H-indene), 3.35, 3.31 (each s, each 2H, CH₂—H), 2.65 (m, 1H,CH-isopropyl), 2.41 (s, 3H CH₃—H), 1.35, 1.33 (each s, each 9H,tert-butyl), 1.15 (d, 6H, isopropyl-CH₃), 0.2, 0.0 (each d, each 3H,SiCH₃).

Dimethylsilanediyl(2-methyl-4-(4′-tert-butylphenyl)indenyl)(2-isopropyl-4-(4′-tert-butylphenyl)indenyl)zirconiumdichloride

36.6 g (60 mmoles) ofdimethylsilanediyl(2-methyl-4-(4′-tert-butylphenyl)-1-indene)(2-isopropyl-4-(4′-tert-butylphenyl)-1-indene)were introduced into 366 ml of diethyl ether, and 44.9 mL of ann-butyllithium solution (2.68 M in toluene) were added withoutinterruption at room temperature. After this addition was complete, themixture was stirred over night at this temperature. It was then cooledto 0° C. and 14.0 g (60 mmoles) of zirconium tetrachloride were added inportions. The mixture was allowed to warm to room temperature and wasstirred for another two hours at this temperature. The precipitate thatforms was separated by filtration through a G3 fritted glass filter andwas washed with two 50 mL portions of tetrahydrofuran and with one 70 mLportion of pentane. The residue was dried in an oil-pump vacuum, and theproduct was obtained in a yield of 23.5 g (50%) and with a rac:mesoratio of about 1:1. The isomers must be separated in a subsequent stepto obtain selective catalysts for propylene polymerization.

¹H-NMR (400 MHz, CDCl₃):

7.7-6.9 (m, 14H, arom-H), 3.26 (m, 1H, CH-isopropyl), 2.23 (s, 3H, CH₃),1.31 (s, 18H, tert-butyl), 1.33, 1.32 (each s, each 3H, Si—CH₃), 1.08,1.03 (each d, each 3H, isopropyl-CH₃).

Preparation of Methylaluminoxane Treated Silica Example 12

To a stirred suspension of 293 g of silica (Grace XPO2107, dried at 180°C. and 1 mbar for 16 hours, LOD<0.5 wt % and LOI=2.6 wt %) in 1500 mL oftoluene is added slowly 300 mL of a 30 wt-% solution ofmethylaluminoxane in toluene (Albemarle Corporation) at roomtemperature. During the addition the temperature must not exceed 30° C.After the addition is complete, the mixture is stirred for two hours atroom temperature and separated by filtration. The residue is washed withtwo 1500 mL portions of toluene and three 1500 mL portions of isohexaneand dried in vacuum to constant weight. The methylaluminoxane treatedsilica is obtained as a free-flowing powder in a yield of 408 g.

Preparation of Supported Metallocene Catalysts Example 13

10.0 g of the methylaluminoxane treated silica prepared in Example 12are placed in a fritted glass filter as a column with a smooth surface.A minimal amount of toluene is added and the treated silica is carefullystirred with a spatula to remove any air pockets in the column. Theexcess toluene is removed by filtration leaving a smooth surface. In aseparate flask 326 mg ofrac-dimethylsilanediyl-bis-(2-(cyclohexylmethyl)-4-(4′-tert-butyl-phenyl)-1-indenyl)-zirconiumdichloride (prepared in Example 1) are mixed with 27 mL of toluene and13.6 mL of a 30 wt-% solution of methylaluminoxane in toluene (AlbemarleCorporation). The slurry is stirred at room temperature for one hour togive an orange solution. This solution is then carefully added on top ofthe methylaluminoxane treated silica and slowly filtered off withinapproximately 30 minutes. When the surface of the colored solutionreaches the top of the silica, the filtration process is stopped and thefilter cake is carefully and thoroughly stirred by means of a spatula.The catalyst is then allowed to rest for one hour. The residual solventis filtered off and the catalyst is washed twice with isohexane (20 mL)and dried in a nitrogen purge to constant weight. The catalyst isobtained as free-flowing reddish powder in a yield of 12.0 g.

Example 14

10.0 g of the methylaluminoxane treated silica prepared in Example 12are placed in a fritted glass filter as a column with a smooth surface.A minimal amount of toluene is added and the treated silica is carefullystirred with a spatula to remove any air pockets in the column. Theexcess toluene is removed by filtration leaving a smooth surface. In aseparate flask 321 mg ofrac-dimethylsilanediyl-bis-(2-(cyclohexylmethyl)-4-(1-naphthyl)-1-indenyl)-zirconiumdichloride (prepared in Example 2) are mixed with 27 mL of toluene and13.6 mL of a 30 wt-% solution of methylaluminoxane in toluene (AlbemarleCorporation). The slurry is stirred at room temperature for one hour togive an orange solution. This solution is then carefully added on top ofthe methylaluminoxane treated silica and slowly filtered off withinapproximately 30 minutes. When the surface of the colored solutionreaches the top of the silica, the filtration process is stopped and thefilter cake is carefully and thoroughly stirred by means of a spatula.The catalyst is then allowed to rest for one hour. The residual solventis filtered off and the catalyst is washed twice with isohexane (20 mL)and dried in a nitrogen purge to constant weight. The catalyst isobtained as free-flowing reddish powder in a yield of 11.8 g.

Example 15

10.0 g of the methylaluminoxane treated silica prepared in Example 12are placed in a fritted glass filter as a column with a smooth surface.A minimal amount of toluene is added and the treated silica is carefullystirred with a spatula to remove any air pockets in the column. Theexcess toluene is removed by filtration leaving a smooth surface. In aseparate flask 295 mg ofrac-dimethylsilanediyl-bis-(2-(cyclohexylmethyl)-4-(4′-methylphenyl)-1-indenyl)-zirconiumdichloride (prepared in Example 3) are mixed with 27 mL of toluene and13.6 mL of a 30 wt-% solution of methylaluminoxane in toluene (AlbemarleCorporation). The slurry is stirred at room temperature for one hour togive an orange solution. This solution is then carefully added on top ofthe methylaluminoxane treated silica and slowly filtered off withinapproximately 30 minutes. When the surface of the colored solutionreaches the top of the silica, the filtration process is stopped and thefilter cake is carefully and thoroughly stirred by means of a spatula.The catalyst is then allowed to rest for one hour. The residual solventis filtered off and the catalyst is washed twice with isohexane (20 mL)and dried in a nitrogen purge to constant weight. The catalyst isobtained as free-flowing reddish powder in a yield of 11.0 g.

Example 16

10.0 g of the methylaluminoxane treated silica prepared in Example 12are placed in a flitted glass filter as a column with a smooth surface.A minimal amount of toluene is added and the treated silica is carefullystirred with a spatula to remove any air pockets in the column. Theexcess toluene is removed by filtration leaving a smooth surface. In aseparate flask 305 mg ofrac-dimethylsilanediyl-bis-(2-(cyclohexylmethyl)-4-(3′,5′-dimethylphenyl)-1-indenyl)-zirconiumdichloride (prepared in Example 4) are mixed with 27 mL of toluene and13.6 mL of a 30 wt-% solution of methylaluminoxane in toluene (AlbemarleCorporation). The slurry is stirred at room temperature for one hour togive an orange solution. This solution is then carefully added on top ofthe methylaluminoxane treated silica and slowly filtered off withinapproximately 30 minutes. When the surface of the colored solutionreaches the top of the silica, the filtration process is stopped and thefilter cake is carefully and thoroughly stirred by means of a spatula.The catalyst is then allowed to rest for one hour. The residual solventis filtered off and the catalyst is washed twice with isohexane (20 mL)and dried in a nitrogen purge to constant weight. The catalyst isobtained as free-flowing reddish powder in a yield of 12.1 g.

Example 17

10.0 g of the methylaluminoxane treated silica prepared in Example 12are placed in a fritted glass filter as a column with a smooth surface.A minimal amount of toluene is added and the treated silica is carefullystirred with a spatula to remove any air pockets in the column. Theexcess toluene is removed by filtration leaving a smooth surface. In aseparate flask 307 mg ofrac-dimethylsilanediyl-bis-(2-(tert-butylmethyl)-4-(4′-tent-butylphenyl)-1-indenyl)-zirconiumdichloride (prepared in Example 5) are mixed with 27 mL of toluene and13.6 mL of a 30 wt-% solution of methylaluminoxane in toluene (AlbemarleCorporation). The slurry is stirred at room temperature for one hour togive an orange solution. This solution is then carefully added on top ofthe methylaluminoxane treated silica and slowly filtered off withinapproximately 30 minutes. When the surface of the colored solutionreaches the top of the silica, the filtration process is stopped and thefilter cake is carefully and thoroughly stirred by means of a spatula.The catalyst is then allowed to rest for one hour. The residual solventis filtered off and the catalyst is washed twice with isohexane (20 mL)and dried in a nitrogen purge to constant weight. The catalyst isobtained as free-flowing reddish powder in a yield of 11.4 g.

Example 18

10.0 g of the methylaluminoxane treated silica prepared in Example 12are placed in a fritted glass filter as a column with a smooth surface.A minimal amount of toluene is added and the treated silica is carefullystirred with a spatula to remove any air pockets in the column. Theexcess toluene is removed by filtration leaving a smooth surface. In aseparate flask 363 mg ofrac-dimethylsilanediyl-bis-(2-(1-adamantylmethyl)-4-(4′-tert-butylphenyl)-1-indenyl)-zirconiumdichloride (prepared in Example 6) are mixed with 27 mL of toluene and13.6 mL of a 30 wt-% solution of methylaluminoxane in toluene (AlbemarleCorporation). The slurry is stirred at room temperature for one hour togive an orange solution. This solution is then carefully added on top ofthe methylaluminoxane treated silica and slowly filtered off withinapproximately 30 minutes. When the surface of the colored solutionreaches the top of the silica, the filtration process is stopped and thefilter cake is carefully and thoroughly stirred by means of a spatula.The catalyst is then allowed to rest for one hour. The residual solventis filtered off and the catalyst is washed twice with isohexane (20 mL)and dried in a nitrogen purge to constant weight. The catalyst isobtained as free-flowing reddish powder in a yield of 11.8 g.

Example 19

10.0 g of the methylaluminoxane treated silica prepared in Example 12are placed in a fritted glass filter as a column with a smooth surface.A minimal amount of toluene is added and the treated silica is carefullystirred with a spatula to remove any air pockets in the column. Theexcess toluene is removed by filtration leaving a smooth surface. In aseparate flask 333 mg ofrac-(n-propyl)(methyl)silanediyl-bis-(2-(cyclohexylmethyl)-4-(4′-tert-butyl-phenyl)-1-indenyl)-zirconiumdichloride (prepared in Example 7) are mixed with 27 mL of toluene and13.6 mL of a 30 wt-% solution of methylaluminoxane in toluene (AlbemarleCorporation). The slurry is stirred at room temperature for one hour togive an orange solution. This solution is then carefully added on top ofthe methylaluminoxane treated silica and slowly filtered off withinapproximately 30 minutes. When the surface of the colored solutionreaches the top of the silica, the filtration process is stopped and thefilter cake is carefully and thoroughly stirred by means of a spatula.The catalyst is then allowed to rest for one hour. The residual solventis filtered off and the catalyst is washed twice with isohexane (20 mL)and dried in a nitrogen purge to constant weight. The catalyst isobtained as free-flowing reddish powder in a yield of 10.7 g.

Comparative Example 20

10.0 g of the methylaluminoxane treated silica prepared in Example 12are placed in a flitted glass filter as a column with a smooth surface.A minimal amount of toluene is added and the treated silica is carefullystirred with a spatula to remove any air pockets in the column. Theexcess toluene is removed by filtration leaving a smooth surface. In aseparate flask 171 mg ofrac-dimethylsilanediyl-bis-(2-methylindenyl)-zirconium dichloride(prepared in Comparative Example 8) are mixed with 27 mL of toluene and13.6 mL of a 30 wt-% solution of methylaluminoxane in toluene (AlbemarleCorporation). The slurry is stirred at room temperature for one hour togive an orange solution. This solution is then carefully added on top ofthe methylaluminoxane treated silica and slowly filtered off withinapproximately 30 minutes. When the surface of the colored solutionreaches the top of the silica, the filtration process is stopped and thefilter cake is carefully and thoroughly stirred by means of a spatula.The catalyst is then allowed to rest for one hour. The residual solventis filtered off and the catalyst is washed twice with isohexane (20 mL)and dried in a nitrogen purge to constant weight. The catalyst isobtained as free-flowing reddish powder in a yield of 12.2 g.

Comparative Example 21

10.0 g of the methylaluminoxane treated silica prepared in Example 12are placed in a fritted glass filter as a column with a smooth surface.A minimal amount of toluene is added and the treated silica is carefullystirred with a spatula to remove any air pockets in the column. Theexcess toluene is removed by filtration leaving a smooth surface. In aseparate flask 207 mg ofrac-dimethylsilanediyl-bis-(2-methyl-4,5-benzoindenyl)-zirconiumdichloride (prepared in Comparative Example 9) are mixed with 27 mL oftoluene and 13.6 mL of a 30 wt-% solution of methylaluminoxane intoluene (Albemarle Corporation). The slurry is stirred at roomtemperature for one hour to give an orange solution. This solution isthen carefully added on top of the methylaluminoxane treated silica andslowly filtered off within approximately 30 minutes. When the surface ofthe colored solution reaches the top of the silica, the filtrationprocess is stopped and the filter cake is carefully and thoroughlystirred by means of a spatula. The catalyst is then allowed to rest forone hour. The residual solvent is filtered off and the catalyst iswashed twice with isohexane (20 mL) and dried in a nitrogen purge toconstant weight. The catalyst is obtained as free-flowing orange powderin a yield of 11.5 g.

Comparative Example 22

10.0 g of the methylaluminoxane treated silica prepared in Example 12are placed in a flitted glass filter as a column with a smooth surface.A minimal amount of toluene is added and the treated silica is carefullystirred with a spatula to remove any air pockets in the column. Theexcess toluene is removed by filtration leaving a smooth surface. In aseparate flask 267 mg ofrac-dimethylsilanediyl-bis-(2-methyl-4-(4′-tert-butylphenyl)-1-indenyl)-zirconiumdichloride (prepared in Comparative Example 10) are mixed with 27 mL oftoluene and 13.6 mL of a 30 wt-% solution of methylaluminoxane intoluene (Albemarle Corporation). The slurry is stirred at roomtemperature for one hour to give an orange solution. This solution isthen carefully added on top of the methylaluminoxane treated silica andslowly filtered off within approximately 30 minutes. When the surface ofthe colored solution reaches the top of the silica, the filtrationprocess is stopped and the filter cake is carefully and thoroughlystirred by means of a spatula. The catalyst is then allowed to rest forone hour. The residual solvent is filtered off and the catalyst iswashed twice with isohexane (20 mL) and dried in a nitrogen purge toconstant weight. The catalyst is obtained as free-flowing orange powderin a yield of 11.9 g.

Comparative Example 23

10.0 g of the methylaluminoxane treated silica prepared in Example 12are placed in a fritted glass filter as a column with a smooth surface.A minimal amount of toluene is added and the treated silica is carefullystirred with a spatula to remove any air pockets in the column. Theexcess toluene is removed by filtration leaving a smooth surface. In aseparate flask 277 mg ofrac-dimethylsilanediyl(2-methyl-4-(4′-tert-butylphenyl)indenyl)(2-isopropyl-4-(4′-tert-butylphenyl)indenyl)zirconiumdichloride (prepared in Comparative Example 11) are mixed with 27 mL oftoluene and 13.6 mL of a 30 wt-% solution of methylaluminoxane intoluene (Albemarle Corporation). The slurry is stirred at roomtemperature for one hour to give an orange solution. This solution isthen carefully added on top of the methylaluminoxane treated silica andslowly filtered off within approximately 30 minutes. When the surface ofthe colored solution reaches the top of the silica, the filtrationprocess is stopped and the filter cake is carefully and thoroughlystirred by means of a spatula. The catalyst is then allowed to rest forone hour. The residual solvent is filtered off and the catalyst iswashed twice with isohexane (20 mL) and dried in a nitrogen purge toconstant weight. The catalyst is obtained as free-flowing orange powderin a yield of 11.9 g.

Example 24

To a stirred suspension of 100 g of silica (Grace XPO8001, dried at 180°C. and 1 mbar for 16 hours, LOD<0.5 wt % and LOI=2.5 wt %) in 480 mL oftoluene is added slowly 250 mL of a 30 wt-% solution ofmethylaluminoxane in toluene (Albemarle Corporation) at roomtemperature. During the addition the temperature must not exceed 30° C.After the addition is complete, the mixture is stirred for half an hourat room temperature and then heated and allowed to reflux for fourhours. After cooling down to room temperature the solvent is separatedby filtration. The residue is washed with two 500 mL portions of tolueneand three 500 mL portions of isohexane and dried in vacuum to constantweight. The methylaluminoxane treated silica is obtained as afree-flowing powder in a yield of 180 g.

10.0 g of the methylaluminoxane treated silica are placed in a frittedglass filter as a column with a smooth surface. A minimal amount oftoluene is added and the treated silica is carefully stirred with aspatula to remove any air pockets in the column. The excess toluene isremoved by filtration leaving a smooth surface. In a separate flask 363mg ofrac-dimethylsilanediyl-bis-(2-(1-adamantylmethyl)-4-(4′-tert-butylphenyl)-1-indenyl)zirconiumdichloride (prepared in Example 6) are mixed with 10 mL of toluene and33.4 mL of a 10 wt-% solution of triisobutylaluminum in heptane (AkzoNobel). The slurry is stirred at room temperature for one hour. Thissolution is then carefully added on top of the methylaluminoxane treatedsilica and slowly filtered off within approximately 30 minutes. When thesurface of the colored solution reaches the top of the silica, thefiltration process is stopped and the filter cake is carefully andthoroughly stirred by means of a spatula. The catalyst is then allowedto rest for one hour. The residual solvent is filtered off and thecatalyst is washed twice with isohexane (20 mL) and dried in a nitrogenpurge to constant weight. The catalyst is obtained as free-flowingpowder in a yield of 12 g.

Polymerizations:

Polymerization Procedure (Batch Propylene Homo- and Co-Polymerization):

A dry and nitrogen purged 5 dm³ autoclave equipped with a stirrer ischarged with if desired 100 g of metallocene polymer seed bed.Optionally, a certain amount of hydrogen is metered in.Triisobutylaluminum (1 cm³ of a 10 wt.-% solution in heptane), liquidpropylene (one-half of the total amount used for the run), andoptionally, a certain amount of ethylene are metered in and the mixtureis stirred for at least 5 minutes (stirrer speed 200 rpm) at 20° C. Thensupported metallocene catalyst, suspended in 5 cm³ of white oil, isinjected with liquid propylene (one-half of total amount used for therun). The reactor is heated to the internally measured run temperature(65, 60 or 30° C.) within 11 minutes. The polymerization reaction isallowed to proceed at the run temperature for either 15 or 60 minutes.During the 60 min copolymerization runs the reactor pressure wasmaintained by continuous feeding of ethylene and propylene. Thepolymerization is stopped by releasing the monomer and cooling down thereactor. The polymer is discharged and dried under reduced pressure.

Fifty-eight separate tests of inventive examples and comparativeexamples and the results in the aggregate are shown in Tables 1 and 2.In additions, Tables 3 through 12 have been created to isolate variousreactor conditions.

Analysis of Results

While the invention of the present application is so exceptional that itshows unexpected improvements over the whole class of Metallocenes, theapplicants note that true comparisons of the effect of this inventionmust be evaluated upon metallocenes of similar structure of the indenylgroup at other than the 2 position. Therefore, while part of thisanalysis will make aggregate comparisons between the several inventiveexamples and the comparative examples, individual catalyst comparisonsshould only be made when the substitutions in all positions of theindenyl groups other than the 2 position are the same to ensure thecomparison of apples to apples. Therefore, individual catalystcomparisons should only be made between inventive examples 13, 17 and 18(various β-branched in the two position of the indenyl group) tocomparative examples 22 (straight chain in the two position of theindenyl group) and 23 (α-branched in the two position of the indenyl)because the substitutions in all positions of the indenyl groups otherthan the 2 position are the same.

Table 1 and Table 2 represent the raw data presented by test runs; theremaining tables 3-12 break that data out by the ratio of propylene toethylene (or if it is a propylene homopolymer) and whether hydrogen wasused in the polymerization process.

Propylene Homopolymers

Analysis 1: Production of Propylene Polymers without the EthyleneComonomer and not in the Presence of Hydrogen.

Table 3 shows the results of eight experimental Metallocene catalystsconforming to the requirements of the invention compared to fourcomparative examples. In the aggregate, the catalysts of the presentinvention showed more than a 50% increase in productivity while at thesame time showing more than a 200% increase in Molecular Weight andalmost a two degree Celcius increase in melting point (significant whenthe range of melting points for homopolymer polypropylene is 144 to153). Further the catalysts of the current invention produced productswith an aggregate MFR 2.16 of less than 1.5% of that of the comparativeproducts and an aggregate MFR 5 of just greater than 2% of thecomparative examples. This dramatic drop in MFR indicates a dramaticincrease of Molecular Weight (more than 200%) and opens full access toapplication fields like film, pipe or sheets, where a high MolecularWeight is mandatory.

The individual catalyst comparisons between inventive samples 13, 17 and18 and comparative examples 22 and 23 are just as dramatic. Whenexamples 13, 17 and 18 are compared to comparative example 22, all threeinventive examples exhibit significantly lower MFR 2.16, MFR 5 rates andincreases in Molecular Weight. Specifically for MFR 2.16, the inventiveexamples 13, 17 and 18 show a respective reduction of 60%, and greaterthan 99%, and greater than 99% of the original value of example 22. Forthe MFR 5, the inventive examples 13, 17 and 18 show a respectivereduction of 78%, 89% and greater than 99% of the original value ofexample 22. For the molecular weight, the inventive examples 13, 17 and18 show a respective increase of 16%, 5% and 26% over the originalvalue. Even more surprisingly is that the inventive examples showedthese dramatic improvements in product properties at approximately thesame productivity levels, and in the case of inventive example 13, a 59%increase in productivity.

When examples 13, 17 and 18 are compared to comparative example 23, allthree inventive examples exhibit significantly lower MFR 2.16, MFR 5rates and increases in Molecular Weight. Specifically for MFR 2.16, theinventive examples 13, 17 and 18 show a respective reduction of 88%,greater than 99%, and greater than 99% of the original value of example23. For MFR 5, inventive examples 13, 17 and 18 show a respectivereduction of 90%, 95% and greater than 99% of the original value ofexample 23. For the molecular weight, the inventive examples 13, 17 and18 show a respective increase of 118%, 97% and 137% over the originalvalue. Productivity was also massively enhanced, respectively by a 277%,93% and 103% increase over the original value.

Analysis 2: Production of Propylene Polymers without the EthyleneComonomer and with the Presence of Hydrogen.

Table 4 shows the results of eight experimental Metallocene catalystsconforming to the requirements of the invention compared to fourcomparative examples. However, in this case, hydrogen was added duringthe polymerization process to enhance catalyst productivity and toregulate the Molecular Weight. In the aggregate, the catalysts of thepresent invention showed more than a 94% increase in productivity whileat the same time showing more than a 32% increase in Molecular Weightand almost a one point three degree Celcius increase in melting point(significant when the range of melting points for homopolymerpolypropylene is 146 to 155). Further the catalysts of the currentinvention produced products with an aggregate MFR 2.16 of less than 34%of that of the comparative products and an aggregate MFR 5 of justgreater than 31% of the comparative examples.

The individual catalyst comparisons between inventive samples 13, 17 and18 and comparative examples 22 and 23 again are dramatic.

When examples 13, 17 and 18 are compared to comparative example 23, allthree inventive examples exhibit significantly lower MFR 2.16, MFR 5rates and increases in Molecular Weight. Specifically for MFR 2.16, theinventive examples 13, 17 and 18 show a respective reduction of 76%,60%, and 76% of the original value of example 23. For MFR 5, inventiveexamples 13, 17 and 18 show a respective reduction of 78%, 64% and 80%of the original value of example 23. For the molecular weight, theinventive examples 13, 17 and 18 show a respective increase of 61%, 18%and 65% over the original value. Productivity was also significantlyenhanced, respectively by a 109%, 84% and 84% increase over the originalvalue.

When examples 13, 17 and 18 are compared to comparative example 22,productivity was significantly enhanced, respectively by a 67%, 47% and47% increase over the original value, while making a product comparablecommercial quality. A direct comparison of MFR and Molecular Weightvalues is not applicable in this case. The metallocene of thecomparative example is well known to have a poor response to hydrogen,which would keep the molecular weight high and the MFR's low. Theinventive examples all provide a far superior hydrogen response, whichshould lead to dramatically lower molecular weights and higher MFR's.That the inventive examples provide similar molecular weights and MFRresponses (similar quality products) at far higher productivities, avery unexpected result.

Propylene/Ethylene Copolymers

The properties of products made from the inventive catalysts were testedat various levels of an ethylene/propylene mix to form copolymers. Withthe introduction of a new variable, the propylene to ethylene ration,far fewer datapoints were taken for the copolymers at each ratio becauseresources became limited. In each case the inventive catalyst fromexample 13 was tested, usually against the comparative catalyst fromexample 23. Occasionally other inventive catalysts were tested, butwithout a significant number of inventive catalysts being tested, anaggregate number would not be statistically significant for eachpropylene to ethylene ratio, with the exception of the ratio of 0.38,for which there were numerous data points. However, an analysis wasconducted on the aggregate of all copolymers which shows significant andunexpected results.

Analysis 3: Aggregate Values of all Propylene/Ethylene Copolymers.

Table 5 represents the average values for productivity, MFR andmolecular weight for all test runs of the inventive catalysts when usedto make propylene/ethylene copolymer as compared to the comparativecatalysts when used to make the same. Whenever a value is reported as“less than” or “greater than” a value, that value is adjusted to thenearest number that would make the inventive examples look poorest andthe comparative examples look best. In short, Table 5 is created in amanner to show the worst case for the inventive examples and the bestcase for the comparative examples.

Even with these adjustments, the inventive catalysts, in the aggregate,show dramatic improvement over the comparative catalysts. The aggregateproductivity of the inventive examples when used to make copolymersdemonstrates a small improvement (1.5%) when compared to the comparativeexamples. However, this improvement proves to be quite significant whenit is taken in light of the dramatic improvements to MFR 2.16, MFR 5 andMolecular Weight, all highly desirable qualities. In the aggregate whenmaking copolymers, the inventive catalysts have a MFR 2.16 value that isless than 0.2% of that of the comparative catalysts, demonstrating anextremely significant improvement. Likewise, in the aggregate whenmaking copolymers, the inventive catalysts have a MFR 5 value that is0.5% of that of the comparative catalysts, again demonstrating anextremely significant improvement. In the aggregate when makingcopolymers, the inventive catalysts have an increase in molecular weightof 74% over that of the comparative catalysts. In the aggregate, theinventive catalysts are clearly and unexpected far superior to those ofthe comparative catalysts.

Analysis 4: Production of Propylene/Ethylene Copolymers with aPropylene/Ethylene Ratio of Approximately 48 and without the Presence ofHydrogen.

In this case, only one inventive catalyst (example 13) was testedagainst one comparative catalyst, (example 23), the results beingpresented in Table 6. As before, the inventive catalyst showedsignificant improvements over the comparative catalyst in all measuredlevels. Specifically for MFR 2.16, the inventive example 13 showed a 50%reduction of the original value of example 23. For MFR 5, inventiveexample 13 showed a 45% reduction of the original value of example 23.The molecular weight of the inventive example 13 showed an increase of26% over the original value. Productivity was also significantlyenhanced, with the inventive sample having a 118% increase over thecomparative example's value.

Analysis 5: Production of Propylene/Ethylene Copolymers with aPropylene/Ethylene Ratio of Approximately 31.5 and without the Presenceof Hydrogen.

In this case, two inventive catalyst (examples 13 and 14) and onecomparative catalyst (example 23), were tested, the results beingpresented in Table 7. However, as noted before, the only validcomparison may be made between inventive catalyst (example 13) and thecomparative catalyst (example 23) because the substitutions are the samein all positions other than in 2 position of the indenyl group.Inventive example 14 is not considered in this analysis, nor would it bevalid to do so.

As before, the inventive catalyst showed improvements over thecomparative catalyst in all measured levels. While the MFR 2.16 valuewas the same for both examples, for MFR 5, inventive example 13 showed a14% reduction of the original value of example 23. The molecular weightof the inventive example 13 showed an increase of 11.5% over theoriginal value. Productivity was significantly enhanced, with theinventive sample having a 73% increase over the comparative example'svalue.

Analysis 6: Production of Propylene/Ethylene Copolymers with aPropylene/Ethylene Ratio of Approximately 15.8 and without the Presenceof Hydrogen.

In this case, two inventive catalyst (examples 13 and 14) and onecomparative catalyst (example 23) were tested, the results beingpresented in Table 8. However, as noted before, the only validcomparison may be made between inventive catalyst (example 13) and thecomparative catalyst (example 23) because the substitutions are the samein all positions other than in 2 position of the indenyl group.Inventive example 14 is not considered in this analysis, nor would it bevalid to do so.

In this case, once again the inventive catalyst achieves remarkablybetter productivity (12.5%) while still creating a comparable product ofsimilar commercial value. The significantly increased productivitycombined with the previously mentioned fact that Metallocene catalyststhat are symmetrically substituted in the 2 position are far easier andmore cost effective to make than asymmetrically substituted metallocenesdemonstrate that this is an unexpectedly superior Metallocene catalyst.

Analysis 7: Production of Propylene/Ethylene Copolymers with aPropylene/Ethylene Ratio of Approximately 10.1 and without the Presenceof Hydrogen.

In this case, two inventive catalyst (examples 13 and 14) and onecomparative catalyst (example 23), were tested, the results beingpresented in Table 9. However, as noted before, the only validcomparison may be made between inventive catalyst (example 13) and thecomparative catalyst (example 23) because the substitutions are the samein all positions other than in 2 position of the indenyl group.Inventive example 14 is not considered in this analysis, nor would it bevalid to do so.

As with Analysis 6, the inventive catalyst in this example achievesbetter productivity (1.8%) while still creating a comparable product ofsimilar commercial value. The increased productivity combined with thepreviously mentioned fact that Metallocene catalysts that aresymmetrically substituted in the 2 position are significantly easier andmore cost effective to make than asymmetrically substituted metallocenesdemonstrate that this is an unexpectedly superior Metallocene catalyst.

Analysis 8: Production of Propylene/Ethylene Copolymers with aPropylene/Ethylene Ratio of Approximately 0.5 and without the Presenceof Hydrogen.

In this case, two inventive catalyst (examples 13 and 19) and onecomparative catalyst (example 21), were tested, the results beingpresented in Table 10. However, as noted before, the only validcomparison may be made between inventive catalyst with substitutionsthat are the same in all positions other than in 2 position of theindenyl group. These cases do not provide any opportunity forcomparative analysis, but are provided for informational purposes only.

Analysis 9: Production of Propylene/Ethylene Copolymers with aPropylene/Ethylene Ratio of Approximately 0.5 and without the Presenceof Hydrogen.

In this case, two inventive catalyst (examples 13 and 19) and twocomparative catalyst (examples 20 and 21), were tested, the resultsbeing presented in Table 11. However, as noted before, the only validcomparison may be made between inventive catalyst with substitutionsthat are the same in all positions other than in 2 position of theindenyl group. These cases do not provide any opportunity forcomparative analysis, but are provided for informational purposes only.

Analysis 10: Production of Propylene/Ethylene Copolymers with aPropylene/Ethylene Ratio of Approximately 0.5 and without the Presenceof Hydrogen.

Table 12 shows the results of eight experimental Metallocene catalystsconforming to the requirements of the invention compared to fourcomparative examples. In the aggregate, the catalysts of the presentinvention showed more than a 525% increase in Molecular Weight. Furtherthe catalysts of the current invention produced products with anaggregate MFR 2.16 of less than 0.15% of that of the comparativeproducts and an aggregate MFR 5 of just greater than 0.43% of thecomparative examples. The productivity of these samples could not bedetermined in these cases because in all of these examples andcomparative examples amorphous propylene/ethylene rubbers have beenproduced. Such polymers generally stick to the autoclave walls and tothe stirrer and a quantitative discharge of the autoclave was notpossible which makes the determination of the productivities unreliable.Commercially, polymers containing such rubber components are produced ina two step polymerisation where in a first step a homo polymer isproduced and in a second step the rubber is produced. This measurereduces the stickiness of the material and allows the commercialproduction and use of such important materials for applications wherelow temperature toughness is required (applications like bumpers forcars, refrigerator and deep freezer food packaging, crates and pails).

The individual catalyst comparisons between inventive samples 13, 17 and18 and comparative examples 22 are just as dramatic. (Recall, othercomparisons would not be valid due to alternative substitutions in allpositions other than in 2 position of the indenyl group). When examples13, 17 and 18 are compared to comparative example 22, all threeinventive examples exhibit significantly lower MFR 2.16 and MFR 5 rates.The Molecular Weights stayed the same or increased. Specifically for MFR2.16, the inventive examples 13, 17 and 18 show a respective reductionof 34%, 98%, and greater than 99% of the original value of example 22.For the MFR 5, the inventive examples 13, 17 and 18 show a respectivereduction of 36%, 98%, and greater than 99% of the original value ofexample 22. For the molecular weight, the inventive examples 13 producedthe same molecular weight of comparative example 22 and examples 17 and18 show a respective increase of 159% and 347% over the original value.

The examples of the inventive catalyst consistently show dramaticimprovement over the comparative examples in gains of productivity andmolecular weight, and reductions in the MFR values.

TABLE 1 Polymerisations Polym. Polym. Productivity Poly. Catalyst H2 C3C2 Catalyst Temp. Time Yield [g polymer/g Example from [mg] [g] [g] [mg][° C.] [min] [g] catalyst*hour] 1 Ex 13 — 1838 — 61 65 60 478 7,800 2 Ex13 50 1837 — 55 65 60 1117 19,900 3 Ex 13 50 1837 — 43 65 60 820 19,1004 Ex 13 — 1192 25 30 60 60 183 6,100 5 Ex 13 — 1182 38 30 60 60 1354,500 6 Ex 13 — 1836 60 75 65 15 190 10,100 7 Ex 13 1185 75 30 60 60 1083,600 8 Ex 13 — 1115 110 30 60 60 98 3,300 9 Ex 13 — 1767 120 75 65 15195 10,400 10 Ex 13 — 1700 180 75 65 15 210 11,200 11 Ex 13 — 55 100 5060 60 12 Ex 13 — 55 125 50 60 60 13 Ex 13 — 55 142 50 60 60 14 Ex 14 —1838 — 107 65 60 152 1,420 15 Ex 14 50 1836 — 76 65 60 318 4,180 16 Ex14 — 1185 38 60 60 60 73 1,220 17 Ex 14 — 1174 75 60 60 60 75 1,250 18Ex 14 — 1099 110 60 60 60 65 1,080 19 Ex 14 — 55 142 50 60 60 20 Ex 15 —1838 — 100 65 60 350 3500 21 Ex 15 50 1837 — 50 65 60 510 10200 22 Ex 15— 55 142 50 60 60 23 Ex 16 — 1837 — 106 65 60 318 3000 24 Ex 16 50 1837— 47 65 60 478 10200 25 Ex 16 — 55 142 50 60 60 26 Ex 17 — 1837 — 105 6560 422 4000 27 Ex 17 50 1836 — 26 65 60 457 17500 28 Ex 17 — 55 142 5060 60 29 Ex 18 — 1837 — 97 65 60 410 4200 30 Ex 18 50 1836 — 30 65 60490 17500 31 Ex 18 — 55 142 50 60 60 32 Ex 19 — 1836 — 103 65 60 3036000 33 Ex 19 50 1837 — 62 65 60 604 18300 34 Ex 19 — 55 100 50 60 60 35Ex 19 — 55 125 50 60 60 36 Ex 19 — 55 142 50 60 60 37 Comp 20 — 1837 —100 65 60 210 2,100 38 Comp 20 50 1834 — 65 65 60 194 5,970 39 Comp 20 —55 100 50 60 60 waxy material 40 Comp 20 — 55 125 50 60 60 waxy material41 Comp 20 — 55 142 50 60 60 waxy material 42 Comp 21 — 1838 — 101 65 60369 3,650 43 Comp 21 50 1837 — 82 65 60 525 6,400 44 Comp 21 — 55 100 5060 60 waxy material 45 Comp 21 — 55 125 50 60 60 waxy material 46 Comp21 — 55 142 50 60 60 waxy material 47 Comp 22 — 1830 — 105 65 60 5174,920 48 Comp 22 50 1830 — 56 65 60 667 11,910 49 Comp 22 — 55 142 50 6060 50 Comp 23 — 1836 — 104 65 60 215 2,070 51 Comp 23 50 1834 — 61 65 60581 9,520 52 Comp 23 — 1200 25 50 60 60 140 2,800 53 Comp 23 — 1200 3850 60 60 130 2,600 54 Comp 23 — 1184 75 50 60 60 160 3,200 55 Comp 23 —1115 110 50 60 60 162 3,240 56 Ex 24 — 1835 — 45 65 60 383 8510 57 Ex 2450 1835 — 20 65 60 730 36500 58 Ex 24 — 55 142 25 60 60

TABLE 2 Polymer Properties: Catalyst Poly. From C2 Tm MFR 2.16 MFR 5 MwExample Example [wt %] [deg C.] [g/10′] [g/10′] [kg/mol] Mw/Mn 1 Ex 13 —151 0.14 0.4 846 3.4 2 Ex 13 — 151 11 34 235 2.6 4 Ex 13 1.3 140 0.2 0.9582 2.7 5 Ex 13 1.7 137 0.3 1.2 544 2.5 6 Ex 13 2.1 135 0.5 1.7 523 2.97 Ex 13 3.8 123 0.8 3.0 413 2.6 8 Ex 13 5.7 111 0.6 2.5 454 2.9 9 Ex 134.3 118 0.8 3.1 422 2.9 10 Ex 13 6.5 103 0.4 1.5 491 2.8 11 Ex 13 39.7amorphous 6.9 21 280 2.7 12 Ex 13 49.1 amorphous 11.5 35 188 2.8 13 Ex13 56.0 amorphous 16.7 51.5 166 2.6 14 Ex 14 — 150 <0.1 <0.1 1311 3.6 15Ex 14 — 150 7.5 20 271 2.8 16 Ex 14 1.5 141 <0.1 <0.1 1240 3.6 17 Ex 143.4 126 <0.1 <0.1 1176 3.6 18 Ex 14 5.0 114 <0.1 <0.1 1226 4.2 19 Ex 1453.5 amorphous 6.9 22 281 3.5 20 Ex 15 — 150 0.18 0.5 652 3.0 21 Ex 15 —150 12 35 191 2.4 22 Ex 15 53.8 amorphous 18 56 164 2.8 23 Ex 16 — 1520.12 0.35 709 2.6 24 Ex 16 — 151 17.4 53 208 2.5 25 Ex 16 55.8 amorphous16 52 172 2.6 26 Ex 17 — 151 <0.1 0.2 763 2.7 27 Ex 17 — 150 18 55 1722.3 28 Ex 17 57.1 amorphous 0.5 1.7 440 2.7 29 Ex 18 — 152 <0.1 <0.1 9202.6 30 Ex 18 — 153 11 30 241 2.6 31 Ex 18 56.0 amorphous <0.1 0.2 7602.7 32 Ex 19 — 150 <0.1 0.25 812 3.3 33 Ex 19 — 151 10 32 225 2.7 36 Ex19 54.7 amorphous 16.5 51 172 2.9 37 Comp 20 — 147 14 44 185 2.7 38 Comp20 — 148 29 98 166 2.6 39 Comp 20 39.5 amorphous n.m. n.m <20 41 Comp 2053.7 amorphous n.m n.m <20 42 Comp 21 — 144 4.3 14 317 2.6 43 Comp 21 —146 64 200 146 2.2 44 Comp 21 32.5 amorphous n.m. n.m <20 46 Comp 2145.7 amorphous n.m n.m <20 47 Comp 22 151 0.35 1.8 730 4.0 48 Comp 22151 4.3 12 216 3.9 49 Comp 22 49.5 amorphous 25.4 81.0 170 3.3 50 Comp23 — 153 1.2 4.0 387 2.8 51 Comp 23 — 155 45.3 152 146 2.4 52 Comp 231.5 142 0.4 1.62 461 2.8 53 Comp 23 2.2 140 0.3 1.4 488 2.7 54 Comp 233.8 125 0.25 0.8 532 2.8 55 Comp 23 5.9 108 <0.1 <0.1 725 2.8 56 Ex 24 —152 <0.1 <0.1 917 2.5 57 Ex 24 — 153 10 31 238 2.5 58 Ex 24 54.0amorphous <0.1 0.2 790 2.4

TABLE 3 Propylene, NO Hydrogen, NO Ethylene Polym. Polym. ProductivityTest Catalyst H2 C3 C2 Catalyst Temp. Time Yield [g polymer/g RunExample [mg] [g] [g] [mg] [° C.] [min] [g] catalyst*hour] 1 Ex 13 — 1838— 61 65 60 478 7,800 14 Ex 14 — 1838 — 107 65 60 152 1,420 20 Ex 15 —1838 — 100 65 60 350 3500 23 Ex 16 — 1837 — 106 65 60 318 3000 26 Ex 17— 1837 — 105 65 60 422 4000 29 Ex 18 — 1837 — 97 65 60 410 4200 32 Ex 19— 1836 — 103 65 60 303 6000 56 Ex 24 — 1835 — 45 65 60 383 8510 37 Comp20 — 1837 — 100 65 60 210 2,100 42 Comp 21 — 1838 — 101 65 60 369 3,65047 Comp 22 — 1830 — 105 65 60 517 4,920 50 Comp 23 — 1836 — 104 65 60215 2,070 Average Experimental 4804 Average Comparative 3185 Test C2 TmMFR 2.16 MFR 5 Mw Run [wt %] [deg C.] [g/10′] [g/10′] [kg/mol] Mw/Mn 1 —151 0.14 0.4 846 3.4 14 — 150 <0.1 <0.1 1311 3.6 20 — 150 0.18 0.5 652 323 — 152 0.12 0.35 709 2.6 26 — 151 <0.1 0.2 763 2.7 29 — 152 <0.1 <0.1920 2.6 32 — 150 <0.1 0.25 812 3.3 56 — 152 <0.1 <0.1 917 2.5 37 — 14714 44 185 2.7 42 — 144 4.3 14 317 2.6 47 151 0.35 1.8 730 4 50 — 153 1.24 387 2.8 Average Experimental 151 0.06 0.34 866.25 2.96 AverageComparative 148 4.96 15.95 404.75 3.03

TABLE 4 Propylene, Hydrogen, NO Ethylene Polym. Polym. Productivity TestCatalyst H2 C3 C2 Catalyst Temp. Time Yield [g polymer/g Run from [mg][g] [g] [mg] [° C.] [min] [g] catalyst*hour] 2 Ex 13 50 1837 — 55 65 601117 19,900 3 Ex 13 50 1837 — 43 65 60 820 19,100 15 Ex 14 50 1836 — 7665 60 318 4,180 21 Ex 15 50 1836 — 50 65 60 510 10200 24 Ex 16 50 1837 —47 65 60 478 10200 27 Ex 17 50 1836 — 26 65 60 457 17500 30 Ex 18 501836 — 30 65 60 490 17500 33 Ex 19 50 1837 — 62 65 60 604 18300 57 Ex 2450 1835 — 20 65 60 730 36500 38 Comp 20 50 1834 — 65 65 60 194 5,970 43Comp 21 50 1837 — 82 65 60 525 6,400 48 Comp 22 50 1830 — 56 65 60 66711,910 51 Comp 23 50 1834 — 61 65 60 581 9,520 Average Experimental16,373 Average Comparative 8,450 Test C2 Tm MFR 2.16 MFR 5 Mw Run [wt %][deg C.] [g/10′] [g/10′] [kg/mol] Mw/Mn 2 — 151 11 34 235 2.6 3 NR NR NRNR 15 — 150 7.5 20 271 2.8 21 — 150 12 35 191 2.4 24 — 151 17.4 53 2082.5 27 — 150 18 55 172 2.3 30 — 153 11 30 241 2.6 33 — 151 10 32 225 2.757 — 153 10 31 238 2.5 38 — 148 29 98 166 2.6 43 — 146 64 200 146 2.2 48151 4.3 12 216 3.9 51 — 155 45.3 152 146 2.4 Average Experimental 15112.11 36.25 222.63 2.55 Average Comparative 150 35.65 115.50 168.50 2.78

TABLE 5 Aggregate Summary of All Copolymer Values Productivity [gpolymer/g C2 Tm MFR 2.16 MFR 5 Mw catalyst*hour] [wt %] [deg C.] [g/10′][g/10′] [kg/mol] Mw/Mn Average Experimental 3,007 6 21 532 3 AverageComparative 2,960 4,289 3,761 305 3

TABLE 6 Propylene/Ethylene ratio ~48, No Hydrogen Polym. Polym.Productivity Test Catalyst H2 C3 C2 Catalyst Temp. Time Yield [gpolymer/g Run from [mg] [g] [g] [mg] [° C.] [min] [g] catalyst*hour] 4Ex 13 — 1192 25 30 60 60 183 6,100 52 Comp 23 — 1200 25 50 60 60 1402,800 Test C2 Tm MFR 2.16 MFR 5 Mw Run [wt %] [deg C.] [g/10′] [g/10′][kg/mol] Mw/Mn 4 1.3 140 0.2 0.9 582 2.7 52 1.5 142 0.4 1.62 461 2.8

TABLE 7 Propylene/Ethylene ratio ~31.5, No Hydrogen Polym. Polym.Productivity Test Catalyst H2 C3 C2 Catalyst Temp. Time Yield [gpolymer/g Run from [mg] [g] [g] [mg] [° C.] [min] [g] catalyst*hour] 5Ex 13 — 1182 38 30 60 60 135 4,500 16 Ex 14 — 1185 38 60 60 60 73 1,22053 Comp 23 — 1200 38 50 60 60 130 2,600 Test C2 Tm MFR 2.16 MFR 5 Mw Run[wt %] [deg C.] [g/10′] [g/10′] [kg/mol] Mw/Mn 5 1.7 137 0.3 1.2 544 2.516 1.5 141 <0.1 <0.1 1240 3.6 53 2.2 140 0.3 1.4 488 2.7

TABLE 8 Propylene/Ethylene ratio ~15.8, No Hydrogen Polym. Polym.Productivity Test Catalyst H2 C3 C2 Catalyst Temp. Time Yield [gpolymer/g Run from [mg] [g] [g] [mg] [° C.] [min] [g] catalyst*hour] 7Ex 13 1185 75 30 60 60 108 3,600 17 Ex 14 — 1174 75 60 60 60 75 1,250 54Comp 23 — 1184 75 50 60 60 160 3,200 Test C2 Tm MFR 2.16 MFR 5 Mw Run[wt %] [deg C.] [g/10′] [g/10′] [kg/mol] Mw/Mn 7 3.8 123 0.8 3 413 2.617 3.4 126 <0.1 <0.1 1176 3.6 54 3.8 125 0.25 0.8 532 2.8

TABLE 9 Propylene/Ethylene ratio ~10.1, No Hydrogen Polym. Polym.Productivity Test Catalyst H2 C3 C2 Catalyst Temp. Time Yield [gpolymer/g Run from [mg] [g] [g] [mg] [° C.] [min] [g] catalyst*hour] 8Ex 13 — 1115 110 30 60 60 98 3,300 18 Ex 14 — 1099 110 60 60 60 65 1,08055 Comp 23 — 1115 110 50 60 60 162 3,240 Test C2 Tm MFR 2.16 MFR 5 MwRun [wt %] [deg C.] [g/10′] [g/10′] [kg/mol] Mw/Mn 8 5.7 111 0.6 2.5 4542.9 18 5 114 <0.1 <0.1 1226 4.2 55 5.9 108 <0.1 <0.1 725 2.8

TABLE 10 Propylene/Ethylene ratio ~.5, No Hydrogen Polym. Polym.Productivity Test Catalyst H2 C3 C2 Catalyst Temp. Time Yield [gpolymer/g Run from [mg] [g] [g] [mg] [° C.] [min] [g] catalyst*hour] 11Ex 13 — 55 100 50 60 60 34 Ex 19 — 55 100 50 60 60 44 Comp 21 — 55 10050 60 60 waxy material Test C2 Tm MFR 2.16 MFR 5 Mw Run [wt %] [deg C.][g/10′] [g/10′] [kg/mol] Mw/Mn 11 39.7 amorphous 6.9 21 280 2.7 34amorphous 44 32.5 amorphous >10000 >10000 <20

TABLE 11 Propylene/Ethylene ratio ~.44, No Hydrogen Polym. Polym.Productivity Test Catalyst H2 C3 C2 Catalyst Temp. Time Yield [gpolymer/g Run from [mg] [g] [g] [mg] [° C.] [min] [g] catalyst*hour] 12Ex 13 — 55 125 50 60 60 35 Ex 19 — 55 125 50 60 60 40 Comp 20 — 55 12550 60 60 waxy material 45 Comp 21 — 55 125 50 60 60 waxy material TestC2 Tm MFR 2.16 MFR 5 Mw Run [wt %] [deg C.] [g/10′] [g/10′] [kg/mol]Mw/Mn 12 49.1 amorphous 11.5 35 188 2.8 35 40 45

TABLE 12 Propylene/Ethylene ratio ~.38, No Hydrogen Polym. Polym.Productivity Poly. Catalyst H2 C3 C2 Catalyst Temp. Time Yield [gpolymer/g Example from [mg] [g] [g] [mg] [° C.] [min] [g] catalyst*hour]13 Ex 13 — 55 142 50 60 60 19 Ex 14 — 55 142 50 60 60 22 Ex 15 — 55 14250 60 60 25 Ex 16 — 55 142 50 60 60 28 Ex 17 — 55 142 50 60 60 31 Ex 18— 55 142 50 60 60 36 Ex 19 — 55 142 50 60 60 58 Ex 24 — 55 142 25 60 6041 Comp 20 — 55 142 50 60 60 waxy material 46 Comp 21 — 55 142 50 60 60waxy material 49 Comp 22 — 55 142 50 60 60 Average Experimental AverageComparative Poly. C2 Tm MFR 2.16 MFR 5 Mw Example [wt %] [deg C.][g/10′] [g/10′] [kg/mol] Mw/Mn 13 56 amorphous 16.7 51.5 166 2.6 19 53.5amorphous 6.9 22 281 3.5 22 53.8 amorphous 18 56 164 2.8 25 55.8amorphous 16 52 172 2.6 28 57.1 amorphous 0.5 1.7 440 2.7 31 56amorphous <0.1 0.2 760 2.7 36 54.7 amorphous 16.5 51 172 2.9 58 54amorphous <0.1 0.2 790 2.4 41 53.7 amorphous >10000 >10000 <20 46 45.7amorphous >10000 >10000 <20 49 49.5 amorphous 25.4 81 170 3.3 AverageExperimental 9.35 29.33 368.13 2.78 Average Comparative 6675.13 6693.6770 3.3

While the above description contains many specifics, these specificsshould not be construed as limitations of the invention, but merely asexemplifications of embodiments thereof. Those skilled in the art willenvision many other embodiments within the scope and spirit of theinvention as defined by the claims appended hereto.

1. A bridged metallocene having the general Formula 1 below,

where M¹ is a metal of Group IVb of the Periodic Table of the Elements,R¹ and R² are identical or different and are each a hydrogen atom, analkyl group of from 1 to about 10 carbon atoms, an alkoxy group of from1 to about 10 carbon atoms, an aryl group of from 6 to about 20 carbonatoms, an aryloxy group of from 6 to about 10 carbon atoms, an alkenylgroup of from 2 to about 10 carbon atoms, an OH group, a halogen atom,or a NR₂ ³² group, where R³² is an alkyl group of from 1 to about 10carbon atoms or an aryl group of from 6 to about 14 carbon atoms and R¹and R² may form one or more ring system(s), R⁴ and R^(4′) are identicalor different and are each a hydrogen atom, a linear, cyclic or branchedhydrocarbon group optionally containing one or more hetero atomsselected from the group consisting of Si, B, Al, O, S, N, P, F, Cl andBr, R¹⁰ is a bridging group wherein R¹⁰ is selected from:

where R⁴⁰ and R⁴¹, even when bearing the same index, can be identical ordifferent and can optionally contain heteroatoms selected from the groupconsisting of Si, B, Al, O, S, N, P, Cl and Br, and are each a hydrogenatom, an alkyl group having from 1 to about 30 carbon atoms, an arylgroup of from 6 to about 40 carbon atoms, a fluoroalkyl group of from 1to about 10 carbon atoms, an alkoxy group of from 1 to about 10 carbonatoms, an aryloxy group of from 6 to about 10 carbon atoms, an alkenylgroup of from 2 to about 10 carbon atoms, an arylalkyl group of from 7to about 40 carbon atoms, an alkylaryl group of from 7 to about 40carbon atoms, a substituted or unsubstituted alkylsilyl, analkyl(aryl)silyl group, an arylsilyl group, or an arylalkenyl group offrom 8 to about 40 carbon atoms or wherein R⁴⁰ and R⁴¹ together with theatoms connecting them can form one or more cyclic systems, x is aninteger from 1 to 18, M¹² is silicon, germanium or tin, and R¹⁰ canoptionally link two units of the formula 1 to one another, R¹¹ andR^(11′) are identical or different and are each a divalent C₂-C₄₀ groupwhich together with the cyclopentadienyl ring forms a further saturatedor unsaturated ring system having a ring size of from 5 to 7 atoms,where R¹¹ and R^(11′) optionally contain the heteroatoms Si, Ge, N, P, Oor S within the ring system fused onto the cyclopentadienyl ring, R³⁰⁰is a —CH₂—CR³⁰¹R³⁰²R³⁰³ or a —CH═CR³⁰²R³⁰³ group, where R³⁰¹, R³⁰² andR³⁰³ are identical or different and/or R³⁰² and R³⁰³ together may form aring system and/or R³⁰¹, R³⁰² and R³⁰³ together may form a ring system,and R³⁰¹, R³⁰², R³⁰³ are each a hydrogen atom, or a linear, cyclic orbranched hydrocarbon group selected from an alkyl group of from 1 toabout 20 carbon atoms, an alkenyl group of from 2 to about 20 carbonatoms, an aryl group of from 6 to about 20 carbon atoms, an arylalkylgroup of from 7 to about 40 carbon atoms, an alkylaryl group of from 7to about 40 carbon atoms, or an arylalkenyl group of from 8 to about 40carbon atoms, an alkoxy group of from 1 to about 20 carbon atoms, anaryloxy group of from 6 to about 20 carbon atoms, or a substituted orunsubstituted alkylsilyl group, an alkyl(aryl)silyl group or anarylsilyl group, wherein the groups optionally contain one or morehetero atoms selected from the group consisting of Si, B, Al, O, S, N,P, F, Cl and Br, with the proviso, that R³⁰² and R³⁰³ are not both ahydrogen atom. R³ has the meaning of R³⁰⁰ or R³ is a hydrogen atom, alinear, cyclic or branched hydrocarbon group which optionally cancontain one or more hetero atoms selected from the group consisting ofSi, B, Al, O, S, N, P, F, Cl or Br and/or wherein R³ is an alkyl groupof from 1 to about 20 carbon atoms, an alkylalkenyl group of from 3 toabout 20 carbon atoms, an alkylaryl group of from 7 to about 40 carbonatoms, or an alkylarylalkenyl group of from 9 to about 40 carbon atoms,with the proviso that R³ is not cyclic or branched in the α-position. 2.The metallocene of claim 1 wherein R¹ and R² are identical or differentand are an alkyl group of from 1 to about 10 carbon atoms, an alkoxygroup of from 1 to about 10 carbon atoms, an aryloxy group of from 6 toabout 10 carbon atoms or a halogen atom, or R¹ and R² together may formone or more ring system(s), and M¹ is zirconium or hafnium.
 3. Themetallocene of claim 1 wherein R¹ and R² are identical or different andare methyl, chlorine or phenolate.
 4. The metallocene of claim 1 whereinR⁴ and/or R^(4′) are a hydrogen atom, an alkyl group of from 1 to 20carbon atoms, an alkenyl group of from 2 to 20 carbon atoms, an arylgroup of from 6 to 20 carbon atoms, an arylalkyl group of from 7 to 40carbon atoms, an alkylaryl group of from 8 to about 40 carbon atoms, anarylalkenyl group of from 8 to about 40 carbon atoms, a substituted orunsubstituted alkylsilyl group, an alkyl(aryl)silyl group, or anarylsilyl group.
 5. The metallocene of claim 1 wherein R⁴ and/or R^(4′)are a hydrogen atom, an alkyl group of from 1 to about 10 carbon atoms,an alkenyl group of from 2 to about 10 carbon atoms, an aryl group offrom 6 to about 10 carbon atoms, an arylalkyl group of from 7 to about20 carbon atoms, an alkylaryl group of from 8 to about 20 carbon atoms,an arylalkenyl group of from 8 to about 20 carbon atoms, a substitutedor unsubstituted alkylsilyl group, an alkyl(aryl)silyl group, or anarylsilyl group.
 6. The metallocene of claim 1 wherein R⁴ and R^(4′) areboth hydrogen.
 7. The metallocene of claim 1 wherein R¹⁰ is R⁴⁰R⁴¹Si═,R⁴⁰R⁴¹Ge═, R⁴⁰R⁴¹C═ or —(R⁴⁰R⁴¹C—CR⁴⁰R⁴¹)—, where R⁴⁰ and R⁴¹ areidentical or different and are each a hydrogen atom, an alkyl group offrom 1 to about 10 carbon atoms, an aryl group of from 6 to about 40carbon atoms, an arylalkyl group of from 7 to about 14 carbon atoms, analkylaryl group of from 7 to about 14 carbon atoms, a substituted orunsubstituted alkylsilyl group, an alkyl(aryl)silyl group, or anarylsilyl group.
 8. The metallocene of claim 1 wherein the bridging unitR¹⁰ is R⁴⁰R⁴¹Si═ or R⁴⁰R⁴¹Ge═, where R⁴⁰ and R⁴¹ are identical ordifferent and are methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl,octyl, nonyl, decyl, undecyl, dodecyl, cyclopentyl, cyclopentadienyl,cyclohexyl, phenyl, naphthyl, benzyl, trimethylsilyl or3,3,3-trifluoropropyl.
 9. The metallocene of claim 1 wherein the groupsR¹¹ and R^(11′) are identical or different and are each a divalent groupselected from those given in Formulae 1 α′, β, γ, δ, φ, and ν andFormulae 1 α′, β′, γ′, δ′, φ′, and ν′, respectively, wherein theasterisks “*” and “**” in Formula 1 and Formulae 1 α-ν and 1 α′-ν′,respectively, denote the chemical bonds joining R¹¹ and R^(11′) to thecyclopentadienyl rings

wherein R⁵, R⁶, R⁷, R⁸, and R⁹ and also R^(5′), R^(6′), R^(7′), R^(8′)and R^(9′) as well as R⁵⁵, R⁶⁶, R⁷⁷, R⁸⁸ and R⁹⁹ and also R^(55′),R^(66′), R^(77′), R^(88′) and R^(99′) are identical or different and areeach a hydrogen atom, a linear, cyclic or branched hydrocarbon groupwith or without heteroatoms selected from the group consisting of Si, B,Al, O, S, N, P, F, Cl and Br, and wherein said R⁵, R⁶, R⁷, R⁸, R⁹,R^(5′), R^(6′), R^(7′), R^(8′), R^(9′), R⁵⁵, R⁶⁶, R⁷⁷, R⁸⁸, R⁹⁹,R^(55′), R^(66′), R^(77′), R^(88′) and R^(99′) are individually selectedfrom an alkyl group of from 2 to about 20 carbon atoms, an alkenyl groupof from 2 to about 20 carbon atoms, an aryl group of from 6 to about 40carbon atoms, an arylalkyl group of from 7 to about 40 carbon atoms, analkylaryl group of from 7 to about 40 carbon atoms, or an arylalkenylgroup of from 8 to about 40 carbon atoms or a substituted orunsubstituted alkylsilyl group, an alkyl(aryl)silyl group or anarylsilyl group, or wherein two adjacent radicals R⁵, R⁶ or R^(5′),R^(6′) or R⁶, R⁷ or R^(6′), R^(7′) or R⁷, R⁸ or R^(7′), R^(8′) or R⁸, R⁹or R^(8′), R^(9′) as well as R⁵⁵, R⁶⁶ or R^(55′), R^(66′) or R⁶⁶, R⁷⁷ orR^(66′), R^(77′) or R⁷⁷, R⁸⁸ or R^(77′), R^(88′) or R⁸⁸, R⁹⁹ or R^(88′),R^(99′) in each case may form a saturated or unsaturated hydrocarbonring system.
 10. The metallocene of claim 9 wherein R¹¹ and R^(11′) areidentical or different and R¹¹ is a divalent group according to Formula1γ and R^(11′) is selected from the divalent groups in Formulae 1α′, β′,and γ′, or R¹¹ and R^(11′) are identical or different and are divalentgroups according to Formula 1α and 1α′ or Formula 1β and 1β′ or Formula1γ and 1γ′ or Formula 1δ and 1δ′ or Formula 1φ and 1φ′ or Formula 1ν and1ν′, respectively.
 11. The metallocene of claim 9 wherein R⁵⁵, R⁶⁶, R⁷⁷,R⁸⁸ and R⁹⁹ and also R^(55′), R^(66′), R^(77′), R^(88′) and R^(99′) areeach a hydrogen atom and R⁵, R⁶, R⁷, R⁸ and R⁹ and also R^(5′), R^(6′),R^(7′), R^(8′) and R^(9′) are identical or different and are each ahydrogen atom, a substituted or unsubstituted alkylsilyl or arylsilylgroup, a linear, cyclic or branched alkyl group of from 1 to about 10carbon atoms, or an aryl group of from 6 to about 40 carbon atoms andthe groups may contain one or more hetero atoms selected from the groupconsisting of Si, B, Al, O, S, N, P, F, Cl and Br, or wherein the twoadjacent radicals R⁵/R⁶ and R^(5′)/R^(6′) form a hydrocarbon ringsystem, or R⁵ and R^(5′) are identical or different and are each asubstituted or unsubstituted aryl group of from 6 to about 40 carbonatoms.
 12. The metallocene of claim 9 wherein R⁵⁵, R⁶⁶, R⁷⁷, R⁸⁸ and R⁹⁹and R^(55′), R^(66′), R^(77′), R^(88′) and R^(99′) are each a hydrogenatom and R⁵, R⁶, R⁷, R⁸ and R⁹ and R^(5′), R^(6′), R^(7′), R^(8′) andR^(9′) are identical or different and are each a hydrogen atom or alinear, cyclic or branched alkyl group of from 1 to about 10 carbonatoms, or an aryl group of from 6 to about 40 carbon atoms, or whereinthe two adjacent radicals R⁵, R⁶ and also R^(5′), R^(6′) together form aring system, or R⁵ and R^(5′) are identical or different and are each asubstituted or unsubstituted aryl group of from 6 to about 40 carbonatoms.
 13. The metallocene of claim 1 wherein R³⁰⁰ is a—CH₂—CR³⁰¹R³⁰²R³⁰³ group, where R³⁰¹, R³⁰² and R³⁰³ are identical ordifferent, wherein R³⁰¹, R³⁰², R³⁰³ are each a hydrogen atom, a linear,cyclic or branched hydrocarbon group which may optionally behalogenated, or R³⁰² and R³⁰³ together may form a ring system, or R³⁰¹,R³⁰² and R³⁰³ together may form a ring system, with the proviso, thatR³⁰² and R³⁰³ are not a hydrogen atom.
 14. The metallocene of claim 13wherein R³⁰¹, R³⁰², R³⁰³ are each individually selected from an alkylgroup of from 1 to about 20 carbon atoms, an alkenyl group of from 2 toabout 20 carbon atoms, an aryl group of from 6 to about 20 carbon atoms,an arylalkyl group of from 7 to about 40 carbon atoms, an alkylarylgroup of from 7 to about 40 carbon atoms, an alkoxy group of from 1 toabout 20 carbon atoms, an aryloxy group of from 6 to about 20 carbonatoms, or an arylalkenyl group of from 8 to about 40 carbon atoms. 15.The metallocene of claim 1 wherein R³⁰⁰ is a —CH₂—CR³⁰¹R³⁰²R³⁰³ group,where R³⁰¹ is a hydrogen atom and where R³⁰² and R³⁰³ are identical ordifferent and R³⁰² and R³⁰³ are each a linear, cyclic or branchedhydrocarbon group which may optionally be halogenated, or R³⁰² and R³⁰³together may form a ring system, with the proviso, that R³⁰⁰ containsmore than 6 carbon atoms.
 16. The metallocene of claim 15, wherein R³⁰²and/or R³⁰³ are each individually selected from an alkyl group of from 1to about 10 carbon atoms, an alkenyl group of from 2 to about 10 carbonatoms, an aryl group of from 6 to about 10 carbon atoms, an arylalkylgroup of from 7 to about 20 carbon atoms, an alkylaryl group of from 7to about 20 carbon atoms, an alkoxy group of from 1 to about 10 carbonatoms, an aryloxy group of from 6 to about 20 carbon atoms, or anarylalkenyl group of from 8 to about 20 carbon atoms.
 17. Themetallocene of claim 1, wherein R³⁰⁰ is a —CH₂—CR³⁰¹R³⁰²R³⁰³ group,where R³⁰¹ and R³⁰² and R³⁰³ are identical or different and/or R³⁰² andR³⁰³ together may form a ring system, and/or R³⁰¹, R³⁰² and R³⁰³together may form a ring system, and R³⁰¹, R³⁰², R³⁰³ are each a linear,cyclic or branched hydrocarbon group which may be halogenated, forexample an alkyl group of from 1 to about 10 carbon atoms, an alkenylgroup of from 2 to about 10 carbon atoms, an aryl group of from 6 toabout 10 carbon atoms, an arylalkyl group of from 7 to about 20 carbonatoms, an alkylaryl group of from 7 to about 20 carbon atoms, anarylalkenyl group of from 8 to about 20 carbon atoms, an alkoxy group offrom 1 to about 10 carbon atoms or an aryloxy group of from 6 to about20 carbon atoms, with the proviso, that R³⁰⁰ contains more than 6 carbonatoms.
 18. The metallocene of claim 1 wherein R³ has the meaning of R³⁰⁰or R³ is a linear, cyclic or branched hydrocarbon group of from 1 toabout 20 carbon atoms, with the proviso that R³ is not cyclic orbranched in the α-position.
 19. The metallocene of claim 18 wherein R³is an alkyl group of from 1 to 20 carbon atoms, an alkylaryl group offrom 7 to about 20 carbon atoms, an alkylalkenyl group of from 3 toabout 20 carbon atoms or an alkylarylalkenyl group of from 9 to about 20carbon atoms.
 20. The metallocene of claim 1 wherein R³ and R³⁰⁰ areidentical or R³ is a methyl group or a linear, cyclic or branchedhydrocarbon group of from 7 to about 10 carbon atoms which mayoptionally be halogenated, an alkylaryl group of from 7 to about 10carbon atoms or an alkylalkenyl group of from 3 to about 10 carbonatoms, with the proviso that R³ is not cyclic or branched in α-position.21. The metallocene of claim 1 wherein R³ and R³⁰⁰ are identical and area —CH₂—CR³⁰¹R³⁰²R³⁰³ group, where R³⁰¹, R³⁰² and R³⁰³ are identical ordifferent and/or R³⁰² and R³⁰³ together may form a ring system, and/orR³⁰¹, R³⁰² and R³⁰³ together may form a ring system, and are each ahydrogen atom, a linear, cyclic or branched hydrocarbon group which maybe halogenated, said hydrocarbon group being selected from an alkylgroup of from 1 to about 20 carbon atoms, an alkenyl group of from 2 toabout 20 carbon atoms, an aryl group of from 6 to about 20 carbon atoms,an arylalkyl group of from 7 to about 40 carbon atoms, an alkylarylgroup of from 7 to about 40 carbon atoms, an arylalkenyl group of from 8to about 40 carbon atoms, an alkoxy group of from 1 to about 10 carbonatoms, and an aryloxy group of from 6 to about 20 carbon atoms, with theproviso, that R³⁰² and R³⁰³ are not a hydrogen atom.
 22. The metalloceneof claim 1 wherein R³ and R³⁰⁰ are identical and are a—CH₂—CR³⁰¹R³⁰²R³⁰³ group, where R³⁰³ is a hydrogen atom and where R³⁰¹and R³⁰² are identical or different and/or R³⁰² and R³⁰³ together mayform a ring system, and are each a linear, cyclic or branchedhydrocarbon group which may optionally be halogenated, said hydrocarbongroup being selected from an alkyl group of from 1 to about 10 carbonatoms, an alkenyl group of from 2 to about 10 carbon atoms, an arylalkylgroup of from 7 to about 20 carbon atoms, an alkylaryl group of from 7to about 20 carbon atoms, an arylalkenyl group of from 8 to about 20carbon atoms, an alkoxy group of from 1 to about 10 carbon atoms and anaryloxy group of from 6 to about 20 carbon atoms, with the proviso thatR³ and R³⁰⁰ contain more than 6 carbon atoms.
 23. The metallocene ofclaim 1 wherein R³ and R³⁰⁰ are identical and are a —CH₂—CR³⁰¹R³⁰²R³⁰³group, where R³⁰³ and R³⁰¹ and R³⁰² are identical or different and/orR³⁰² and R³⁰³ together may form a ring system, and are each a linear,cyclic or branched hydrocarbon group which may be halogenated and isselected from an alkyl group of from 1 to about 10 carbon atoms, analkenyl group of from 2 to about 10 carbon atoms, an arylalkyl group offrom 7 to about 20 carbon atoms, an alkylaryl group of from 7 to about20 carbon atoms, an arylalkenyl group of from 8 to about 20 carbonatoms, an alkoxy group of from 1 to about 10 carbon atoms and an aryloxygroup of from 6 to about 20 carbon atoms, with the proviso that R³ andR³⁰⁰ contain more than 6 carbon atoms.
 24. The metallocene of claim 1wherein R³ and R³⁰⁰ are identical and are a —CH₂—CR³⁰¹R³⁰²R³⁰³ group,where R³⁰³ and R³⁰¹ and R³⁰² are identical or different and/or R³⁰¹,R³⁰² and R³⁰³ together may form a ring system, and are each a linear,cyclic or branched hydrocarbon group which may be halogenated, forexample an alkyl group of from 1 to about 10 carbon atoms, an alkenylgroup of from 2 to about 10 carbon atoms, an arylalkyl group of from 7to about 20 carbon atoms, an alkylaryl group of from 7 to about 20carbon atoms, an arylalkenyl group of from 8 to about 20 carbon atoms,an alkoxy group of from 1 to about 10 carbon atoms, or an aryloxy groupof from 6 to about 20 carbon atoms, with the proviso that R³ and R³⁰⁰contain more than 6 carbon atoms.
 25. A process for olefinpolymerisation comprising contacting one or more olefins each havingfrom 2 to about 20 carbon atoms under olefin polymerisation reactionconditions with a catalyst system including a bridged metallocenecomponent having formula 1

where M¹ is a metal of Group IVb of the Periodic Table of the Elements,R¹ and R² are identical or different and are each a hydrogen atom, analkyl group of from 1 to about 10 carbon atoms, an alkoxy group of from1 to about 10 carbon atoms, an aryl group of from 6 to about 20 carbonatoms, an aryloxy group of from 6 to about 10 carbon atoms, an alkenylgroup of from 2 to about 10 carbon atoms, an OH group, a halogen atom,or a NR₂ ³² group, where R³² is an alkyl group of from 1 to about 10carbon atoms or an aryl group of from 6 to about 14 carbon atoms and R¹and R² may form one or more ring system(s), R⁴ and R^(4′) are identicalor different and are each a hydrogen atom, a linear, cyclic or branchedhydrocarbon group optionally containing one or more hetero atomsselected from the group consisting of Si, B, Al, O, S, N, P, F, Cl andBr, R¹⁰ is a bridging group wherein R¹⁰ is selected from:

where R⁴⁰ and R⁴¹, even when bearing the same index, can be identical ordifferent and can optionally contain heteroatoms selected from the groupconsisting of Si, B, Al, O, S, N, P, Cl and Br, and are each a hydrogenatom, an alkyl group having from 1 to about 30 carbon atoms, an arylgroup of from 6 to about 40 carbon atoms, a fluoroalkyl group of from 1to about 10 carbon atoms, an alkoxy group of from 1 to about 10 carbonatoms, an aryloxy group of from 6 to about 10 carbon atoms, an alkenylgroup of from 2 to about 10 carbon atoms, an arylalkyl group of from 7to about 40 carbon atoms, an alkylaryl group of from 7 to about 40carbon atoms, a substituted or unsubstituted alkylsilyl, analkyl(aryl)silyl group, an arylsilyl group, or an arylalkenyl group offrom 8 to about 40 carbon atoms or wherein R⁴⁰ and R⁴¹ together with theatoms connecting them can form one or more cyclic systems, x is aninteger from 1 to 18, M¹² is silicon, germanium or tin, and R¹⁰ canoptionally link two units of the formula 1 to one another, R¹¹ andR^(11′) are identical or different and are each a divalent C₂-C₄₀ groupwhich together with the cyclopentadienyl ring forms a further saturatedor unsaturated ring system having a ring size of from 5 to 7 atoms,where R¹¹ and R^(11′) optionally contain the heteroatoms Si, Ge, N, P, Oor S within the ring system fused onto the cyclopentadienyl ring, R³⁰⁰is a —CH₂—CR³⁰¹R³⁰²R³⁰³ or a —CH═CR³⁰²R³⁰³ group, where R³⁰¹, R³⁰² andR³⁰³ are identical or different and/or R³⁰² and R³⁰³ together may form aring system and/or R³⁰¹, R³⁰² and R³⁰³ together may form a ring system,and R³⁰¹, R³⁰², R³⁰³ are each a hydrogen atom, or a linear, cyclic orbranched hydrocarbon group selected from an alkyl group of from 1 toabout 20 carbon atoms, an alkenyl group of from 2 to about 20 carbonatoms, an aryl group of from 6 to about 20 carbon atoms, an arylalkylgroup of from 7 to about 40 carbon atoms, an alkylaryl group of from 7to about 40 carbon atoms, or an arylalkenyl group of from 8 to about 40carbon atoms, an alkoxy group of from 1 to about 20 carbon atoms, anaryloxy group of from 6 to about 20 carbon atoms, or a substituted orunsubstituted alkylsilyl group, an alkyl(aryl)silyl group or anarylsilyl group, wherein the groups optionally contain one or morehetero atoms selected from the group consisting of Si, B, Al, O, S, N,P, F, Cl and Br, with the proviso, that R³⁰² and R³⁰³ are not both ahydrogen atom. R³ has the meaning of R³⁰⁰ or R³ is a hydrogen atom, alinear, cyclic or branched hydrocarbon group which optionally cancontain one or more hetero atoms selected from the group consisting ofSi, B, Al, O, S, N, P, F, Cl and Br, and/or wherein R³ is an alkyl groupof from 1 to about 20 carbon atoms, an alkylalkenyl group of from 3 toabout 20 carbon atoms, an alkylaryl group of from 7 to about 40 carbonatoms, or an alkylarylalkenyl group of from 9 to about 40 carbon atoms,with the proviso that R³ is not cyclic or branched in the α-position.26. The process of claim 25 wherein R¹ and R² are identical or differentand are an alkyl group of from 1 to about 10 carbon atoms, an alkoxygroup of from 1 to about 10 carbon atoms, an aryloxy group of from 6 toabout 10 carbon atoms or a halogen atom, or R¹ and R² together may formone or more ring system(s), and M¹ is zirconium or hafnium.
 27. Theprocess of claim 25 wherein R¹ and R² are identical or different and aremethyl, chlorine or phenolate.
 28. The process of claim 25 wherein R⁴and/or R^(4′) are a hydrogen atom, an alkyl group of from 1 to 20 carbonatoms, an alkenyl group of from 2 to 20 carbon atoms, an aryl group offrom 6 to 20 carbon atoms, an arylalkyl group of from 7 to 40 carbonatoms, an alkylaryl group of from 8 to about 40 carbon atoms, anarylalkenyl group of from 8 to about 40 carbon atoms, a substituted orunsubstituted alkylsilyl group, an alkyl(aryl)silyl group, or anarylsilyl group.
 29. The process of claim 25 wherein R⁴ and/or R^(4′)are a hydrogen atom, an alkyl group of from 1 to about 10 carbon atoms,an alkenyl group of from 2 to about 10 carbon atoms, an aryl group offrom 6 to about 10 carbon atoms, an arylalkyl group of from 7 to about20 carbon atoms, an alkylaryl group of from 8 to about 20 carbon atoms,an arylalkenyl group of from 8 to about 20 carbon atoms, a substitutedor unsubstituted alkylsilyl group, an alkyl(aryl)silyl group, or anarylsilyl group.
 30. The process of claim 25 wherein R⁴ and R^(4′) areboth hydrogen.
 31. The process of claim 25 wherein R¹⁰ is R⁴⁰R⁴¹Si═,R⁴⁰R⁴¹Ge═, R⁴⁰R⁴¹C═ or —(R⁴⁰R⁴¹C—CR⁴⁰R⁴¹)—, where R⁴⁰ and R⁴¹ areidentical or different and are each a hydrogen atom, an alkyl group offrom 1 to about 10 carbon atoms, an aryl group of from 6 to about 40carbon atoms, an arylalkyl group of from 7 to about 14 carbon atoms, analkylaryl group of from 7 to about 14 carbon atoms, a substituted orunsubstituted alkylsilyl group, an alkyl(aryl)silyl group, or anarylsilyl group.
 32. The process of claim 25 wherein the bridging unitR¹⁰ is R⁴⁰R⁴¹Si═ or R⁴⁰R⁴¹Ge═, where R⁴⁰ and R⁴¹ are identical ordifferent and are methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl,octyl, nonyl, decyl, undecyl, dodecyl, cyclopentyl, cyclopentadienyl,cyclohexyl, phenyl, naphthyl, benzyl, trimethylsilyl or3,3,3-trifluoropropyl.
 33. The process of claim 25 wherein the groupsR¹¹ and R^(11′) are identical or different and are each a divalent groupselected from those given in Formulae 1 α, β, γ, δ, φ, and ν andFormulae 1 α′, β′, γ′, δ′, φ′, and ν′, respectively, wherein theasterisks “*” and “**” in Formula 1 and Formulae 1 α-ν and 1 α′-ν′,respectively, denote the chemical bonds joining R¹¹ and R^(11′) to thecyclopentadienyl rings

wherein R⁵, R⁶, R⁷, R⁸, and R⁹ and also R^(5′), R^(6′), R^(7′), R^(8′)and R^(9′) as well as R⁵⁵, R⁶⁶, R⁷⁷, R⁸⁸ and R⁹⁹ and also R^(55′),R^(66′), R^(77′), R^(88′) and R^(99′) are identical or different and areeach a hydrogen atom, a linear, cyclic or branched hydrocarbon groupwith or without heteroatoms selected from the group consisting of Si, B,Al, O, S, N, P, F, Cl and Br, and wherein said R⁵, R⁶, R⁷, R⁸, R⁹,R^(5′), R^(6′), R^(7′), R^(8′), R^(9′), R⁵⁵, R⁶⁶, R⁷⁷, R⁸⁸, R⁹⁹,R^(55′), R^(66′), R^(77′), R^(88′) and R^(99′) are individually selectedfrom an alkyl group of from 2 to about 20 carbon atoms, an alkenyl groupof from 2 to about 20 carbon atoms, an aryl group of from 6 to about 40carbon atoms, an arylalkyl group of from 7 to about 40 carbon atoms, analkylaryl group of from 7 to about 40 carbon atoms, an arylalkenyl groupof from 8 to about 40 carbon atoms, a substituted or unsubstitutedalkylsilyl group, an alkyl(aryl)silyl group and an arylsilyl group, orwherein two adjacent radicals R⁵, R⁶ or R^(5′), R^(6′) or R⁶, R⁷ orR^(6′), R^(7′) or R⁷, R⁸ or R^(7′), R^(8′) or R⁸, R⁹ or R^(8′), R^(9′)as well as R⁵⁵, R⁶⁶ or R^(55′), R^(66′) or R⁶⁶, R⁷⁷ or R^(66′), R^(77′)or R⁷⁷, R⁸⁸ or R^(77′), R^(88′) or R⁸⁸, R⁹⁹ or R^(88′), R^(99′) in eachcase may form a saturated or unsaturated hydrocarbon ring system. 34.The process of claim 33 wherein R¹¹ and R^(11′) are identical ordifferent and R¹¹ is a divalent group according to Formula 1γ andR^(11′) is selected from the divalent groups in Formulae 1α′, β′, andγ′, or R¹¹ and R^(11′) are identical or different and are divalentgroups according to Formula 1α and 1α′ or Formula 1β and 1β′ or Formula1γ and 1γ′ or Formula 1δ and 1δ′ or Formula 1φ and 1φ′ or Formula 1ν and1ν′, respectively.
 35. The process of claim 33 wherein R⁵⁵, R⁶⁶, R⁷⁷,R⁸⁸ and R⁹⁹ and also R^(55′), R^(66′), R^(77′), R^(88′) and R^(99′) areeach a hydrogen atom and R⁵, R⁶, R⁷, R⁸ and R⁹ and also R^(5′), R^(6′),R^(7′), R^(8′) and R^(9′) are identical or different and are each ahydrogen atom, a substituted or unsubstituted alkylsilyl or arylsilylgroup, a linear, cyclic or branched alkyl group of from 1 to about 10carbon atoms, or an aryl group of from 6 to about 40 carbon atoms andthe groups may contain one or more hetero atoms selected from the groupconsisting of Si, B, Al, O, S, N, P, F, Cl and Br, or wherein the twoadjacent radicals R⁵/R⁶ and R^(5′)/R^(6′) form a hydrocarbon ringsystem, or R⁵ and R^(5′) are identical or different and are each asubstituted or unsubstituted aryl group of from 6 to about 40 carbonatoms.
 36. The process of claim 33 wherein R⁵⁵, R⁶⁶, R⁷⁷, R⁸⁸ and R⁹⁹and R^(55′), R^(66′), R^(77′), R^(88′) and R^(99′) are each a hydrogenatom and R⁵, R⁶, R⁷, R⁸ and R⁹ and R^(5′), R^(6′), R^(7′), R^(8′) andR^(9′) are identical or different and are each a hydrogen atom or alinear, cyclic or branched alkyl group of from 1 to about 10 carbonatoms, or an aryl group of from 6 to about 40 carbon atoms, or whereinthe two adjacent radicals R⁵, R⁶ and also R^(5′), R^(6′) together form aring system, or R⁵ and R^(5′) are identical or different and are each asubstituted or unsubstituted aryl group of from 6 to about 40 carbonatoms.
 37. The process of claim 25 wherein R³⁰⁰ is a —CH₂—CR³⁰¹R³⁰²R³⁰³group, where R³⁰¹, R³⁰² and R³⁰³ are identical or different, whereinR³⁰¹, R³⁰², R³⁰³ are each a hydrogen atom, a linear, cyclic or branchedhydrocarbon group which may optionally be halogenated, or R³⁰² and R³⁰³together may form a ring system, or R³⁰¹, R³⁰² and R³⁰³ together mayform a ring system, with the proviso, that R³⁰² and R³⁰³ are not ahydrogen atom
 38. The process of claim 37 wherein R³⁰¹, R³⁰², R³⁰³ areeach individually selected from an alkyl group of from 1 to about 20carbon atoms, an alkenyl group of from 2 to about 20 carbon atoms, anaryl group of from 6 to about 20 carbon atoms, an arylalkyl group offrom 7 to about 40 carbon atoms, an alkylaryl group of from 7 to about40 carbon atoms, an alkoxy group of from 1 to about 20 carbon atoms, anaryloxy group of from 6 to about 20 carbon atoms, or an arylalkenylgroup of from 8 to about 40 carbon atoms.
 39. The process of claim 25wherein R³⁰⁰ is a —CH₂—CR³⁰¹R³⁰²R³⁰³ group, where R³⁰¹ is a hydrogenatom and where R³⁰² and R³⁰³ are identical or different and R³⁰² andR³⁰³ are each a linear, cyclic or branched hydrocarbon group which mayoptionally be halogenated, or R³⁰² and R³⁰³ together may form a ringsystem, with the proviso, that R³⁰⁰ contains more than 6 carbon atoms.40. The process of claim 39, wherein R³⁰² and/or R³⁰³ are eachindividually selected from an alkyl group of from 1 to about 10 carbonatoms, an alkenyl group of from 2 to about 10 carbon atoms, an arylgroup of from 6 to about 10 carbon atoms, an arylalkyl group of from 7to about 20 carbon atoms, an alkylaryl group of from 7 to about 20carbon atoms, an alkoxy group of from 1 to about 10 carbon atoms, anaryloxy group of from 6 to about 20 carbon atoms, or an arylalkenylgroup of from 8 to about 20 carbon atoms.
 41. The process of claim 25,wherein R³⁰⁰ is a —CH₂—CR³⁰¹R³⁰²R³⁰³ group, where R³⁰¹ and R³⁰² and R³⁰³are identical or different and/or R³⁰² and R³⁰³ together may form a ringsystem, and/or R³⁰¹, R³⁰² and R³⁰³ together may form a ring system, andR³⁰¹, R³⁰², R³⁰³ are each a linear, cyclic or branched hydrocarbongroup, which may optionally be halogenated, and which is selected froman alkyl group of from 1 to about 10 carbon atoms, an alkenyl group offrom 2 to about 10 carbon atoms, an aryl group of from 6 to about 10carbon atoms, an arylalkyl group of from 7 to about 20 carbon atoms, analkylaryl group of from 7 to about 20 carbon atoms, an arylalkenyl groupof from 8 to about 20 carbon atoms, an alkoxy group of from 1 to about10 carbon atoms and an aryloxy group of from 6 to about 20 carbon atoms,with the proviso, that R³⁰⁰ contains more than 6 carbon atoms.
 42. Theprocess of claim 25 wherein R³ has the meaning of R³⁰⁰ or R³ is alinear, cyclic or branched hydrocarbon group of from 1 to about 20carbon atoms, with the proviso that R³ is not cyclic or branched in theα-position.
 43. The process of claim 42 wherein R³ is an alkyl group offrom 1 to 20 carbon atoms, an alkylaryl group of from 7 to about 20carbon atoms, an alkylalkenyl group of from 3 to about 20 carbon atomsor an alkylarylalkenyl group of from 9 to about 20 carbon atoms.
 44. Theprocess of claim 25 wherein R³ and R³⁰⁰ are identical or R³ is a methylgroup or a linear, cyclic or branched hydrocarbon group of from 7 toabout 10 carbon atoms which may optionally be halogenated, an alkylarylgroup of from 7 to about 10 carbon atoms or an alkylalkenyl group offrom 3 to about 10 carbon atoms, with the proviso that R³ is not cyclicor branched in α-position.
 45. The process of claim 25 wherein R³ andR³⁰⁰ are identical and are a —CH₂—CR³⁰¹R³⁰²R³⁰³ group, where R³⁰¹, R³⁰²and R³⁰³ are identical or different and/or R³⁰² and R³⁰³ together mayform a ring system, and/or R³⁰¹, R³⁰² and R³⁰³ together may form a ringsystem, and are each a hydrogen atom, a linear, cyclic or branchedhydrocarbon group which may be halogenated, said hydrocarbon group beingselected from an alkyl group of from 1 to about 20 carbon atoms, analkenyl group of from 2 to about 20 carbon atoms, an aryl group of from6 to about 20 carbon atoms, an arylalkyl group of from 7 to about 40carbon atoms, an alkylaryl group of from 7 to about 40 carbon atoms, anarylalkenyl group of from 8 to about 40 carbon atoms, an alkoxy group offrom 1 to about 10 carbon atoms and an aryloxy group of from 6 to about20 carbon atoms, with the proviso, that R³⁰² and R³⁰³ are not a hydrogenatom.
 46. The process of claim 25 wherein R³ and R³⁰⁰ are identical andare a —CH₂—CR³⁰¹R³⁰²R³⁰³ group, where R³⁰³ is a hydrogen atom and whereR³⁰¹ and R³⁰² are identical or different and/or R³⁰² and R³⁰³ togethermay form a ring system, and are each a linear, cyclic or branchedhydrocarbon group which may optionally be halogenated, said hydrocarbongroup being selected from an alkyl group of from 1 to about 10 carbonatoms, an alkenyl group of from 2 to about 10 carbon atoms, an arylalkylgroup of from 7 to about 20 carbon atoms, an alkylaryl group of from 7to about 20 carbon atoms, an arylalkenyl group of from 8 to about 20carbon atoms, an alkoxy group of from 1 to about 10 carbon atoms and anaryloxy group of from 6 to about 20 carbon atoms, with the proviso thatR³ and R³⁰⁰ contain more than 6 carbon atoms.
 47. The process of claim25, wherein R³ and R³⁰⁰ are identical and are a —CH₂—CR³⁰¹R³⁰²R³⁰³group, where R³⁰³ and R³⁰¹ and R³⁰² are identical or different and/orR³⁰² and R³⁰³ together may form a ring system, and are each a linear,cyclic or branched hydrocarbon group which may be halogenated, forexample an alkyl group of from 1 to about 10 carbon atoms, an alkenylgroup of from 2 to about 10 carbon atoms, an arylalkyl group of from 7to about 20 carbon atoms, an alkylaryl group of from 7 to about 20carbon atoms, an arylalkenyl group of from 8 to about 20 carbon atoms,an alkoxy group of from 1 to about 10 carbon atoms and an aryloxy groupof from 6 to about 20 carbon atoms, with the proviso that R³ and R³⁰⁰contain more than 6 carbon atoms.
 48. The process of claim 25 wherein R³and R³⁰⁰ are identical and are a —CH₂—CR³⁰¹R³⁰²R³⁰³ group, where R³⁰³and R³⁰¹ and R³⁰² are identical or different and/or R³⁰¹, R³⁰² and R³⁰³together may form a ring system, and are each a linear, cyclic orbranched hydrocarbon group which may be halogenated, and which isselected from an alkyl group of from 1 to about 10 carbon atoms, analkenyl group of from 2 to about 10 carbon atoms, an arylalkyl group offrom 7 to about 20 carbon atoms, an alkylaryl group of from 7 to about20 carbon atoms, an arylalkenyl group of from 8 to about 20 carbonatoms, an alkoxy group of from 1 to about 10 carbon atoms, and anaryloxy group of from 6 to about 20 carbon atoms, with the proviso thatR³ and R³⁰⁰ contain more than 6 carbon atoms.
 49. The process of claim25 wherein the olefins include propylene and/or ethylene.
 50. Theprocess of claim 25 wherein the olefins include at least one olefinhaving the formula R^(m)—CH═CH—R^(n) wherein R^(m) and R^(n) can beidentical or different and are each individually a hydrogen atom or aradical having from 1 to about 20 carbon atoms, or R^(m) and R^(n)together can form one or more rings.
 51. The process of claim 25 whereinthe olefins include one or more compounds selected from the groupconsisting of ethylene, propylene, 1-butene, 1-pentene, 1-hexene,4-methyl-1-pentene or 1-octene, styrene, 1,3-butadiene, 1,4-hexadiene,vinylnorbornene, norbornadiene, ethylnorbornadiene, norbornene,tetracyclododecene and methylnorbornene.
 52. A bridged metallocenehaving the general Formula 1a below,

Where M¹, R¹, R², R³, R⁴, R^(4′), R¹⁰ and R³⁰⁰ have the meaning setforth in claim
 1. 53. The metallocene of claim 52, wherein R⁵, R⁶, R⁷and R⁸ and also R^(5′), R^(6′), R^(7′) and R^(8′) are identical ordifferent and are each a hydrogen atom, a linear, cyclic or branchedhydrocarbon group selected from an alkyl group of from 1 to about 20carbon atoms, an alkenyl group of from 2 to about 20 carbon atoms, anaryl group of from 6 to about 40 carbon atoms, an arylalkyl group offrom 7 to about 40 carbon atoms, an alkylaryl group of from 7 to about40 carbon atoms, an arylalkenyl group of from 8 to about 40 carbonatoms, a substituted or unsubstituted alkylsilyl group, analkyl(aryl)silyl group and an arylsilyl group.
 54. The metallocene ofclaim 53, wherein the linear, cyclic or branched hydrocarbon groupscontain one or more hetero atoms selected from the group consisting ofSi, B, Al, O, S, N, P, F, Cl and Br, and/or two adjacent radicals R⁵, R⁶or R⁶, R⁷ or R⁷, R⁸ and also R^(5′), R^(6′) or R^(6′), R^(7′) or R^(7′),R^(8′) in each case may form a hydrocarbon ring system.
 55. Themetallocene of claim 52, wherein R⁵, R⁶, R⁷ and R⁸ and also R^(5′),R^(6′), R^(7′) and R^(8′) are identical or different and are each ahydrogen atom, a substituted or unsubstituted alkylsilyl or arylsilylgroup, a linear, cyclic or branched alkyl group of from 1 to about 10carbon atoms, or an aryl group of from 6 to about 40 carbon atoms andwhere the two adjacent radicals R⁵, R⁶ and also R^(5′), R^(6′) may forma saturated or unsaturated hydrocarbon ring system.
 56. The metalloceneof claim 52, wherein R⁶, R⁷, R⁸ and also R^(6′), R^(7′) and R^(8′) areidentical or different and are each a hydrogen atom, a linear, cyclic orbranched hydrocarbon group selected from an alkyl group of from 1 toabout 10 carbon atoms, an alkenyl group of from 2 to about 10 carbonatoms, an aryl group of from 6 to about 20 carbon atoms, an arylalkylgroup of from 7 to about 40 carbon atoms, an alkylaryl group of from 7to about 40 carbon atoms, an arylalkenyl group of from 8 to about 40carbon atoms, a substituted or unsubstituted alkylsilyl group, analkyl(aryl)silyl group and an arylsilyl group, and/or two adjacentradicals R⁶, R⁷ or R⁷, R⁸ as well as R^(6′), R^(7′) or R^(7′), R^(8′) ineach case may form a hydrocarbon ring system and where R⁵ and R^(5′) areidentical or different and are each a substituted or unsubstituted arylgroup of from 6 to about 40 carbon atoms which may contain one or morehetero atoms selected from the group consisting of Si, B, Al, O, S, N,P, F, Cl and Br.
 57. The metallocene of claim 56, wherein the linear,cyclic or branched hydrocarbon groups may contain one or more heteroatoms selected from the group consisting of Si, B, Al, O, S, N, P, F, Cland Br.
 58. The metallocene of claim 52, wherein R⁶, R⁷ and R⁸ and alsoR^(6′), R^(7′) and R^(8′) are identical or different and are each ahydrogen atom, a substituted or unsubstituted alkylsilyl or arylsilylgroup, a linear, cyclic or branched alkyl group of from 1 to about 10carbon atoms, or an aryl group of from 6 to about 10 carbon atoms, whichmay contain one or more hetero atoms selected from the group consistingof Si, B, Al, O, S, N, P, F, Cl and Br, and where R⁵ and R^(5′) areidentical or different and are each a substituted or unsubstituted arylgroup of from 6 to about 40 carbon atoms.
 59. The metallocene of claim52, wherein R⁶, R⁷ and R⁸ and also R^(6′), R^(7′) and R^(8′) areidentical or different and are each a hydrogen atom or a linear, cyclicor branched alkyl group of from 1 to about 10 carbon atoms, or an arylgroup of from 6 to about 10 carbon atoms and where R⁵ and R^(5′) areidentical or different and are each naphthyl, 4-(C₁-C₁₀-alkyl)phenyl or4-(C₆-C₂₀-aryl)phenyl such as 4-methyl-phenyl, 4-biphenyl,4-ethyl-phenyl, 4-n-propyl-phenyl, 4-isopropyl-phenyl,4-tert-butyl-phenyl, 4-sec-butyl-phenyl, 4-cyclohexyl-phenyl,4-trimethylsilyl-phenyl, 4-adamantyl-phenyl,4-(C₁-C₁₀-fluoroalkyl)-phenyl, 3-(C₁-C₁₀-alkyl)-phenyl,3-(C₁-C₁₀-fluoroalkyl)-phenyl, 3-(C₆-C₂₀-aryl)phenyl like 3-biphenyl,3,5-di-(C₁-C₁₀-alkyl)-phenyl such as 3,5-dimethyl-phenyl,3,5-di-(C₁-C₁₀-fluoroalkyl)-phenyl, such as3,5-di(trifluoromethyl)-phenyl or 3,5-(C₆-C₂₀-aryl)phenyl like3,5-terphenyl.
 60. The metallocene of claim 52 wherein the metalloceneis a compound selected from the group consisting of:Dimethylsilanediylbis[2-t-butylmethyl-4-(1-naphthyl)-indenyl]zirconiumdichloride,Dimethylsilanediylbis[2-t-butylmethyl-4-(2-naphthyl)-indenyl]zirconiumdichloride,Dimethylsilanediylbis[2-t-butylmethyl-4-(4-methyl-phenyl)-indenyl]zirconiumdichloride,Dimethylsilanediylbis[2-t-butylmethyl-4-(4-biphenyl)-indenyl]zirconiumdichloride,Dimethylsilanediylbis[2-t-butylmethyl-4-(4-ethyl-phenyl)-indenyl]zirconiumdichloride,Dimethylsilanediylbis[2-t-butylmethyl-4-(4-n-propyl-phenyl)-indenyl]zirconiumdichloride,Dimethylsilanediylbis[2-t-butylmethyl-4-(4-i-propyl-phenyl)-indenyl]zirconiumdichloride,Dimethylsilanediylbis[2-t-butylmethyl-4-(4-t-butyl-phenyl)-indenyl]zirconiumdichloride,Dimethylsilanediylbis[2-t-butylmethyl-4-(4-sec-butyl-phenyl)-indenyl]zirconiumdichloride,Dimethylsilanediylbis[2-t-butylmethyl-4-(4-cyclohexyl-phenyl)-indenyl]zirconiumdichloride,Dimethylsilanediylbis[2-t-butylmethyl-4-(4-trimethylsilyl-phenyl)-indenyl]zirconiumdichloride,Dimethylsilanediylbis[2-t-butylmethyl-4-(4-adamantyl-phenyl)-indenyl]zirconiumdichloride,Dimethylsilanediylbis[2-t-butylmethyl-4-(3-biphenyl)-indenyl]zirconiumdichloride,Dimethylsilanediylbis[2-t-butylmethyl-4-(3,5-dimethyl-phenyl)-indenyl]zirconiumdichloride,Dimethylsilanediylbis[2-t-butylmethyl-4-(3,5-di-(trifluoromethyl)-phenyl)-indenyl]zirconiumdichloride,Dimethylsilanediylbis[2-t-butylmethyl-4-(3,5-terphenyl)-indenyl]zirconiumdichloride,Dimethylsilanediylbis[2-cyclopentylmethyl-4-(1-naphthyl)-indenyl]zirconiumdichloride,Dimethylsilanediylbis[2-cyclopentylmethyl-4-(2-naphthyl)-indenyl]zirconiumdichloride,Dimethylsilanediylbis[2-cyclopentylmethyl-4-(4-methyl-phenyl)-indenyl]zirconiumdichloride,Dimethylsilanediylbis[2-cyclopentylmethyl-4-(4-biphenyl)-indenyl]zirconiumdichloride,Dimethylsilanediylbis[2-cyclopentylmethyl-4-(4-ethyl-phenyl)-indenyl]zirconiumdichloride,Dimethylsilanediylbis[2-cyclopentylmethyl-4-(4-n-propyl-phenyl)-indenyl]zirconiumdichloride,Dimethylsilanediylbis[2-cyclopentylmethyl-4-(4-i-propyl-phenyl)-indenyl]zirconiumdichloride,Dimethylsilanediylbis[2-cyclopentylmethyl-4-(4-t-butyl-phenyl)-indenyl]zirconiumdichloride,Dimethylsilanediylbis[2-cyclopentylmethyl-4-(4-sec-butyl-phenyl)-indenyl]zirconiumdichloride,Dimethylsilanediylbis[2-cyclopentylmethyl-4-(4-cyclohexyl-phenyl)-indenyl]zirconiumdichloride,Dimethylsilanediylbis[2-cyclopentylmethyl-4-(4-trimethylsilyl-phenyl)-indenyl]zirconiumdichloride,Dimethylsilanediylbis[2-cyclopentylmethyl-4-(4-adamantyl-phenyl)-indenyl]zirconiumdichloride,Dimethylsilanediylbis[2-cyclopentylmethyl-4-(3-biphenyl)-indenyl]zirconiumdichloride,Dimethylsilanediylbis[2-cyclopentylmethyl-4-(3,5-dimethyl-phenyl)-indenyl]zirconiumdichloride,Dimethylsilanediylbis[2-cyclopentylmethyl-4-(3,5-di-(trifluoromethyl)-phenyl)-indenyl]zirconiumdichloride,Dimethylsilanediylbis[2-cyclopentylmethyl-4-(3,5-terphenyl)-indenyl]zirconiumdichloride,Dimethylsilanediylbis[2-cyclohexylmethyl-4-(1-naphthyl)-indenyl]zirconiumdichloride,Dimethylsilanediylbis[2-cyclohexylmethyl-4-(2-naphthyl)-indenyl]zirconiumdichloride,Dimethylsilanediylbis[2-cyclohexylmethyl-4-(4-methyl-phenyl)-indenyl]zirconiumdichloride,Dimethylsilanediylbis[2-cyclohexylmethyl-4-(4-biphenyl)-indenyl]zirconiumdichloride,Dimethylsilanediylbis[2-cyclohexylmethyl-4-(4-ethyl-phenyl)-indenyl]zirconiumdichloride,Dimethylsilanediylbis[2-cyclohexylmethyl-4-(4-n-propyl-phenyl)-indenyl]zirconiumdichloride,Dimethylsilanediylbis[2-cyclohexylmethyl-4-(4-i-propyl-phenyl)-indenyl]zirconiumdichloride,Dimethylsilanediylbis[2-cyclohexylmethyl-4-(4-t-butyl-phenyl)-indenyl]zirconiumdichloride,Dimethylsilanediylbis[2-cyclohexylmethyl-4-(4-sec-butyl-phenyl)-indenyl]zirconiumdichloride,Dimethylsilanediylbis[2-cyclohexylmethyl-4-(4-cyclohexyl-phenyl)-indenyl]zirconiumdichloride,Dimethylsilanediylbis[2-cyclohexylmethyl-4-(4-trimethylsilyl-phenyl)-indenyl]zirconiumdichloride,Dimethylsilanediylbis[2-cyclohexylmethyl-4-(4-adamantyl-phenyl)-indenyl]zirconiumdichloride,Dimethylsilanediylbis[2-cyclohexylmethyl-4-(3-biphenyl)-indenyl]zirconiumdichloride,Dimethylsilanediylbis[2-cyclohexylmethyl-4-(3,5-dimethyl-phenyl)-indenyl]zirconiumdichloride,Dimethylsilanediylbis[2-cyclohexylmethyl-4-(3,5-di-(trifluoromethyl)-phenyl)-indenyl]zirconiumdichloride,Dimethylsilanediylbis[2-cyclohexylmethyl-4-(3,5-terphenyl)-indenyl]zirconiumdichloride,Dimethylsilanediylbis[2-cycloheptylmethyl-4-(1-naphthyl)-indenyl]zirconiumdichloride,Dimethylsilanediylbis[2-cycloheptylmethyl-4-(2-naphthyl)-indenyl]zirconiumdichloride,Dimethylsilanediylbis[2-cycloheptylmethyl-4-(4-methyl-phenyl)-indenyl]zirconiumdichloride,Dimethylsilanediylbis[2-cycloheptylmethyl-4-(4-biphenyl)-indenyl]zirconiumdichloride,Dimethylsilanediylbis[2-cycloheptylmethyl-4-(4-ethyl-phenyl)-indenyl]zirconiumdichloride,Dimethylsilanediylbis[2-cycloheptylmethyl-4-(4-n-propyl-phenyl)-indenyl]zirconiumdichloride,Dimethylsilanediylbis[2-cycloheptylmethyl-4-(4-i-propyl-phenyl)-indenyl]zirconiumdichloride,Dimethylsilanediylbis[2-cycloheptylmethyl-4-(4-t-butyl-phenyl)-indenyl]zirconiumdichloride,Dimethylsilanediylbis[2-cycloheptylmethyl-4-(4-sec-butyl-phenyl)-indenyl]zirconiumdichloride,Dimethylsilanediylbis[2-cycloheptylmethyl-4-(4-cyclohexyl-phenyl)-indenyl]zirconiumdichloride,Dimethylsilanediylbis[2-cycloheptylmethyl-4-(4-trimethylsilyl-phenyl)-indenyl]zirconiumdichloride,Dimethylsilanediylbis[2-cycloheptylmethyl-4-(4-adamantyl-phenyl)-indenyl]zirconiumdichloride,Dimethylsilanediylbis[2-cycloheptylmethyl-4-(3-biphenyl)-indenyl]zirconiumdichloride,Dimethylsilanediylbis[2-cycloheptylmethyl-4-(3,5-dimethyl-phenyl)-indenyl]zirconiumdichloride,Dimethylsilanediylbis[2-cycloheptylmethyl-4-(3,5-di-(trifluoromethyl)-phenyl)-indenyl]zirconiumdichloride,Dimethylsilanediylbis[2-cycloheptylmethyl-4-(3,5-terphenyl)-indenyl]zirconiumdichloride,Dimethylsilanediylbis[2-adamantylmethyl-4-(1-naphthyl)-indenyl]zirconiumdichloride,Dimethylsilanediylbis[2-adamantylmethyl-4-(2-naphthyl)-indenyl]zirconiumdichloride,Dimethylsilanediylbis[2-adamantylmethyl-4-(4-methyl-phenyl)-indenyl]zirconiumdichloride,Dimethylsilanediylbis[2-adamantylmethyl-4-(4-biphenyl)-indenyl]zirconiumdichloride,Dimethylsilanediylbis[2-adamantylmethyl-4-(4-ethyl-phenyl)-indenyl]zirconiumdichloride,Dimethylsilanediylbis[2-adamantylmethyl-4-(4-n-propyl-phenyl)-indenyl]zirconiumdichloride,Dimethylsilanediylbis[2-adamantylmethyl-4-(4-i-propyl-phenyl)-indenyl]zirconiumdichloride,Dimethylsilanediylbis[2-adamantylmethyl-4-(4-t-butyl-phenyl)-indenyl]zirconiumdichloride,Dimethylsilanediylbis[2-adamantylmethyl-4-(4-sec-butyl-phenyl)-indenyl]zirconiumdichloride,Dimethylsilanediylbis[2-adamantylmethyl-4-(4-cyclohexyl-phenyl)-indenyl]zirconiumdichloride,Dimethylsilanediylbis[2-adamantylmethyl-4-(4-trimethylsilyl-phenyl)-indenyl]zirconiumdichloride,Dimethylsilanediylbis[2-adamantylmethyl-4-(4-adamantyl-phenyl)-indenyl]zirconiumdichloride,Dimethylsilanediylbis[2-adamantylmethyl-4-(3-biphenyl)-indenyl]zirconiumdichloride,Dimethylsilanediylbis[2-adamantylmethyl-4-(3,5-dimethyl-phenyl)-indenyl]zirconiumdichloride,Dimethylsilanediylbis[2-adamantylmethyl-4-(3,5-di-(trifluoromethyl)-phenyl)-indenyl]zirconiumdichloride,Dimethylsilanediylbis[2-adamantylmethyl-4-(3,5-terphenyl)-indenyl]zirconiumdichloride,Dimethylsilanediylbis[2-trimethylsilylmethyl-4-(4-t-butyl-phenyl)-indenyl]zirconiumdichloride,Dimethylsilanediylbis[2-(2-methoxy-2-methyl-propyl)-4-(4-t-butyl-phenyl)-indenyl]zirconiumdichloride,Dimethylsilanediylbis[2-(2,6-dimethyl-benzyl)-4-(4-t-butyl-phenyl)-indenyl]zirconiumdichloride,Dimethylsilanediylbis[2-(2,4,6-trimethyl-benzyl)-4-(4-t-butyl-phenyl)-indenyl]zirconiumdichloride,Dimethylsilanediylbis[2-bicyclo[2.2.1]heptylmethyl-4-(1-naphthyl)-indenyl]zirconiumdichloride,Dimethylsilanediylbis[2-bicyclo[2.2.1]heptylmethyl-4-(2-naphthyl)-indenyl]zirconiumdichloride,Dimethylsilanediylbis[2-bicyclo[2.2.1]heptylmethyl-4-(4-methyl-phenyl)-indenyl]zirconiumdichloride,Dimethylsilanediylbis[2-bicyclo[2.2.1]heptylmethyl-4-(4-biphenyl)-indenyl]zirconiumdichloride,Dimethylsilanediylbis[2-bicyclo[2.2.1]heptylmethyl-4-(4-ethyl-phenyl)-indenyl]zirconiumdichloride,Dimethylsilanediylbis[2-bicyclo[2.2.1]heptylmethyl-4-(4-n-propyl-phenyl)-indenyl]zirconiumdichloride,Dimethylsilanediylbis[2-bicyclo[2.2.1]heptylmethyl-4-(4-i-propyl-phenyl)-indenyl]zirconiumdichloride,Dimethylsilanediylbis[2-bicyclo[2.2.1]heptylmethyl-4-(4-t-butyl-phenyl)-indenyl]zirconiumdichloride,Dimethylsilanediylbis[2-bicyclo[2.2.1]heptylmethyl-4-(4-sec-butyl-phenyl)-indenyl]zirconiumdichloride,Dimethylsilanediylbis[2-bicyclo[2.2.1]heptylmethyl-4-(4-cyclohexyl-phenyl)-indenyl]zirconiumdichloride,Dimethylsilanediylbis[2-bicyclo[2.2.1]heptylmethyl-4-(4-trimethylsilyl-phenyl)-indenyl]zirconiumdichloride,Dimethylsilanediylbis[2-bicyclo[2.2.1]heptylmethyl-4-(4-adamantyl-phenyl)-indenyl]zirconiumdichloride,Dimethylsilanediylbis[2-bicyclo[2.2.1]heptylmethyl-4-(3-biphenyl)-indenyl]zirconiumdichloride,Dimethylsilanediylbis[2-bicyclo[2.2.1]heptylmethyl-4-(3,5-dimethyl-phenyl)-indenyl]zirconiumdichloride,Dimethylsilanediylbis[2-bicyclo[2.2.1]heptylmethyl-4-(3,5-di-(trifluoromethyl)-phenyl)-indenyl]zirconiumdichloride,Dimethylsilanediylbis[2-bicyclo[2.2.1]heptylmethyl-4-(3,5-terphenyl)-indenyl]zirconiumdichloride,(Methyl)(n-propyl)silanediylbis[2-t-butylmethyl-4-(1-naphthyl)-indenyl]zirconiumdichloride,(Methyl)(n-propyl)silanediylbis[2-t-butylmethyl-4-(2-naphthyl)-indenyl]zirconiumdichloride,(Methyl)(n-propyl)silanediylbis[2-t-butylmethyl-4-(4-methyl-phenyl)-indenyl]zirconiumdichloride,(Methyl)(n-propyl)silanediylbis[2-t-butylmethyl-4-(4-biphenyl)-indenyl]zirconiumdichloride,(Methyl)(n-propyl)silanediylbis[2-t-butylmethyl-4-(4-ethyl-phenyl)-indenyl]zirconiumdichloride,(Methyl)(n-propyl)silanediylbis[2-t-butylmethyl-4-(4-n-propyl-phenyl)-indenyl]zirconiumdichloride,(Methyl)(n-propyl)silanediylbis[2-t-butylmethyl-4-(4-i-propyl-phenyl)-indenyl]zirconiumdichloride,(Methyl)(n-propyl)silanediylbis[2-t-butylmethyl-4-(4-t-butyl-phenyl)-indenyl]zirconiumdichloride,(Methyl)(n-propyl)silanediylbis[2-t-butylmethyl-4-(4-sec-butyl-phenyl)-indenyl]zirconiumdichloride,(Methyl)(n-propyl)silanediylbis[2-t-butylmethyl-4-(4-cyclohexyl-phenyl)-indenyl]zirconiumdichloride,(Methyl)(n-propyl)silanediylbis[2-t-butylmethyl-4-(4-trimethylsilyl-phenyl)-indenyl]zirconiumdichloride,(Methyl)(n-propyl)silanediylbis[2-t-butylmethyl-4-(4-adamantyl-phenyl)-indenyl]zirconiumdichloride,(Methyl)(n-propyl)silanediylbis[2-t-butylmethyl-4-(3-biphenyl)-indenyl]zirconiumdichloride,(Methyl)(n-propyl)silanediylbis[2-t-butylmethyl-4-(3,5-dimethyl-phenyl)-indenyl]zirconiumdichloride,(Methyl)(n-propyl)silanediylbis[2-t-butylmethyl-4-(3,5-di-(trifluoromethyl)-phenyl)-indenyl]zirconiumdichloride,(Methyl)(n-propyl)silanediylbis[2-t-butylmethyl-4-(3,5-terphenyl)-indenyl]zirconiumdichloride,(Methyl)(n-propyl)silanediylbis[2-cyclopentylmethyl-4-(1-naphthyl)-indenyl]zirconiumdichloride,(Methyl)(n-propyl)silanediylbis[2-cyclopentylmethyl-4-(2-naphthyl)-indenyl]zirconiumdichloride,(Methyl)(n-propyl)silanediylbis[2-cyclopentylmethyl-4-(4-methyl-phenyl)-indenyl]zirconiumdichloride,(Methyl)(n-propyl)silanediylbis[2-cyclopentylmethyl-4-(4-biphenyl)-indenyl]zirconiumdichloride,(Methyl)(n-propyl)silanediylbis[2-cyclopentylmethyl-4-(4-ethyl-phenyl)-indenyl]zirconiumdichloride,(Methyl)(n-propyl)silanediylbis[2-cyclopentylmethyl-4-(4-n-propyl-phenyl)-indenyl]zirconiumdichloride,(Methyl)(n-propyl)silanediylbis[2-cyclopentylmethyl-4-(4-i-propyl-phenyl)-indenyl]zirconiumdichloride,(Methyl)(n-propyl)silanediylbis[2-cyclopentylmethyl-4-(4-t-butyl-phenyl)-indenyl]zirconiumdichloride,(Methyl)(n-propyl)silanediylbis[2-cyclopentylmethyl-4-(4-sec-butyl-phenyl)-indenyl]zirconiumdichloride,(Methyl)(n-propyl)silanediylbis[2-cyclopentylmethyl-4-(4-cyclohexyl-phenyl)-indenyl]zirconiumdichloride,(Methyl)(n-propyl)silanediylbis[2-cyclopentylmethyl-4-(4-trimethylsilyl-phenyl)-indenyl]zirconiumdichloride,(Methyl)(n-propyl)silanediylbis[2-cyclopentylmethyl-4-(4-adamantyl-phenyl)-indenyl]zirconiumdichloride,(Methyl)(n-propyl)silanediylbis[2-cyclopentylmethyl-4-(3-biphenyl)-indenyl]zirconiumdichloride,(Methyl)(n-propyl)silanediylbis[2-cyclopentylmethyl-4-(3,5-dimethyl-phenyl)-indenyl]zirconiumdichloride,(Methyl)(n-propyl)silanediylbis[2-cyclopentylmethyl-4-(3,5-di-(trifluoromethyl)-phenyl)-indenyl]zirconiumdichloride,(Methyl)(n-propyl)silanediylbis[2-cyclopentylmethyl-4-(3,5-terphenyl)-indenyl]zirconiumdichloride,(Methyl)(n-propyl)silanediylbis[2-cyclohexylmethyl-4-(1-naphthyl)-indenyl]zirconiumdichloride,(Methyl)(n-propyl)silanediylbis[2-cyclohexylmethyl-4-(2-naphthyl)-indenyl]zirconiumdichloride,(Methyl)(n-propyl)silanediylbis[2-cyclohexylmethyl-4-(4-methyl-phenyl)-indenyl]zirconiumdichloride,(Methyl)(n-propyl)silanediylbis[2-cyclohexylmethyl-4-(4-biphenyl)-indenyl]zirconiumdichloride,(Methyl)(n-propyl)silanediylbis[2-cyclohexylmethyl-4-(4-ethyl-phenyl)-indenyl]zirconiumdichloride,(Methyl)(n-propyl)silanediylbis[2-cyclohexylmethyl-4-(4-n-propyl-phenyl)-indenyl]zirconiumdichloride,(Methyl)(n-propyl)silanediylbis[2-cyclohexylmethyl-4-(4-i-propyl-phenyl)-indenyl]zirconiumdichloride,(Methyl)(n-propyl)silanediylbis[2-cyclohexylmethyl-4-(4-t-butyl-phenyl)-indenyl]zirconiumdichloride,(Methyl)(n-propyl)silanediylbis[2-cyclohexylmethyl-4-(4-sec-butyl-phenyl)-indenyl]zirconiumdichloride,(Methyl)(n-propyl)silanediylbis[2-cyclohexylmethyl-4-(4-cyclohexyl-phenyl)-indenyl]zirconiumdichloride,(Methyl)(n-propyl)silanediylbis[2-cyclohexylmethyl-4-(4-trimethylsilyl-phenyl)-indenyl]zirconiumdichloride,(Methyl)(n-propyl)silanediylbis[2-cyclohexylmethyl-4-(4-adamantyl-phenyl)-indenyl]zirconiumdichloride,(Methyl)(n-propyl)silanediylbis[2-cyclohexylmethyl-4-(3-biphenyl)-indenyl]zirconiumdichloride,(Methyl)(n-propyl)silanediylbis[2-cyclohexylmethyl-4-(3,5-dimethyl-phenyl)-indenyl]zirconiumdichloride,(Methyl)(n-propyl)silanediylbis[2-cyclohexylmethyl-4-(3,5-di-(trifluoromethyl)-phenyl)-indenyl]zirconiumdichloride,(Methyl)(n-propyl)silanediylbis[2-cyclohexylmethyl-4-(3,5-terphenyl)-indenyl]zirconiumdichloride,(Methyl)(n-propyl)silanediylbis[2-cycloheptylmethyl-4-(1-naphthyl)-indenyl]zirconiumdichloride,(Methyl)(n-propyl)silanediylbis[2-cycloheptylmethyl-4-(2-naphthyl)-indenyl]zirconiumdichloride,(Methyl)(n-propyl)silanediylbis[2-cycloheptylmethyl-4-(4-methyl-phenyl)-indenyl]zirconiumdichloride,(Methyl)(n-propyl)silanediylbis[2-cycloheptylmethyl-4-(4-biphenyl)-indenyl]zirconiumdichloride,(Methyl)(n-propyl)silanediylbis[2-cycloheptylmethyl-4-(4-ethyl-phenyl)-indenyl]zirconiumdichloride,(Methyl)(n-propyl)silanediylbis[2-cycloheptylmethyl-4-(4-n-propyl-phenyl)-indenyl]zirconiumdichloride,(Methyl)(n-propyl)silanediylbis[2-cycloheptylmethyl-4-(4-i-propyl-phenyl)-indenyl]zirconiumdichloride,(Methyl)(n-propyl)silanediylbis[2-cycloheptylmethyl-4-(4-t-butyl-phenyl)-indenyl]zirconiumdichloride,(Methyl)(n-propyl)silanediylbis[2-cycloheptylmethyl-4-(4-sec-butyl-phenyl)-indenyl]zirconiumdichloride,(Methyl)(n-propyl)silanediylbis[2-cycloheptylmethyl-4-(4-cyclohexyl-phenyl)-indenyl]zirconiumdichloride,(Methyl)(n-propyl)silanediylbis[2-cycloheptylmethyl-4-(4-trimethylsilyl-phenyl)-indenyl]zirconiumdichloride,(Methyl)(n-propyl)silanediylbis[2-cycloheptylmethyl-4-(4-adamantyl-phenyl)-indenyl]zirconiumdichloride,(Methyl)(n-propyl)silanediylbis[2-cycloheptylmethyl-4-(3-biphenyl)-indenyl]zirconiumdichloride,(Methyl)(n-propyl)silanediylbis[2-cycloheptylmethyl-4-(3,5-dimethyl-phenyl)-indenyl]zirconiumdichloride,(Methyl)(n-propyl)silanediylbis[2-cycloheptylmethyl-4-(3,5-di-(trifluoromethyl)-phenyl)-indenyl]zirconiumdichloride,(Methyl)(n-propyl)silanediylbis[2-cycloheptylmethyl-4-(3,5-terphenyl)-indenyl]zirconiumdichloride,(Methyl)(n-propyl)silanediylbis[2-adamantylmethyl-4-(1-naphthyl)-indenyl]zirconiumdichloride,(Methyl)(n-propyl)silanediylbis[2-adamantylmethyl-4-(2-naphthyl)-indenyl]zirconiumdichloride,(Methyl)(n-propyl)silanediylbis[2-adamantylmethyl-4-(4-methyl-phenyl)-indenyl]zirconiumdichloride,(Methyl)(n-propyl)silanediylbis[2-adamantylmethyl-4-(4-biphenyl)-indenyl]zirconiumdichloride,(Methyl)(n-propyl)silanediylbis[2-adamantylmethyl-4-(4-ethyl-phenyl)-indenyl]zirconiumdichloride,(Methyl)(n-propyl)silanediylbis[2-adamantylmethyl-4-(4-n-propyl-phenyl)-indenyl]zirconiumdichloride,(Methyl)(n-propyl)silanediylbis[2-adamantylmethyl-4-(4-i-propyl-phenyl)-indenyl]zirconiumdichloride,(Methyl)(n-propyl)silanediylbis[2-adamantylmethyl-4-(4-t-butyl-phenyl)-indenyl]zirconiumdichloride,(Methyl)(n-propyl)silanediylbis[2-adamantylmethyl-4-(4-sec-butyl-phenyl)-indenyl]zirconiumdichloride,(Methyl)(n-propyl)silanediylbis[2-adamantylmethyl-4-(4-cyclohexyl-phenyl)-indenyl]zirconiumdichloride,(Methyl)(n-propyl)silanediylbis[2-adamantylmethyl-4-(4-trimethylsilyl-phenyl)-indenyl]zirconiumdichloride,(Methyl)(n-propyl)silanediylbis[2-adamantylmethyl-4-(4-adamantyl-phenyl)-indenyl]zirconiumdichloride,(Methyl)(n-propyl)silanediylbis[2-adamantylmethyl-4-(3-biphenyl)-indenyl]zirconiumdichloride,(Methyl)(n-propyl)silanediylbis[2-adamantylmethyl-4-(3,5-dimethyl-phenyl)-indenyl]zirconiumdichloride,(Methyl)(n-propyl)silanediylbis[2-adamantylmethyl-4-(3,5-di-(trifluoromethyl)-phenyl)-indenyl]zirconiumdichloride,(Methyl)(n-propyl)silanediylbis[2-adamantylmethyl-4-(3,5-terphenyl)-indenyl]zirconiumdichloride,(Methyl)(n-propyl)silanediylbis[2-bicyclo[2.2.1]heptylmethyl-4-(1-naphthyl)-indenyl]zirconiumdichloride,(Methyl)(n-propyl)silanediylbis[2-bicyclo[2.2.1]heptylmethyl-4-(2-naphthyl)-indenyl]zirconiumdichloride,(Methyl)(n-propyl)silanediylbis[2-bicyclo[2.2.1]heptylmethyl-4-(4-methyl-phenyl)-indenyl]zirconiumdichloride,(Methyl)(n-propyl)silanediylbis[2-bicyclo[2.2.1]heptylmethyl-4-(4-biphenyl)-indenyl]zirconiumdichloride,(Methyl)(n-propyl)silanediylbis[2-bicyclo[2.2.1]heptylmethyl-4-(4-ethyl-phenyl)-indenyl]zirconiumdichloride,(Methyl)(n-propyl)silanediylbis[2-bicyclo[2.2.1]heptylmethyl-4-(4-n-propyl-phenyl)-indenyl]zirconiumdichloride,(Methyl)(n-propyl)silanediylbis[2-bicyclo[2.2.1]heptylmethyl-4-(4-i-propyl-phenyl)-indenyl]zirconiumdichloride,(Methyl)(n-propyl)silanediylbis[2-bicyclo[2.2.1]heptylmethyl-4-(4-t-butyl-phenyl)-indenyl]zirconiumdichloride,(Methyl)(n-propyl)silanediylbis[2-bicyclo[2.2.1]heptylmethyl-4-(4-sec-butyl-phenyl)-indenyl]zirconiumdichloride,(Methyl)(n-propyl)silanediylbis[2-bicyclo[2.2.1]heptylmethyl-4-(4-cyclohexyl-phenyl)-indenyl]zirconiumdichloride,(Methyl)(n-propyl)silanediylbis[2-bicyclo[2.2.1]heptylmethyl-4-(4-trimethylsilyl-phenyl)-indenyl]zirconiumdichloride,(Methyl)(n-propyl)silanediylbis[2-bicyclo[2.2.1]heptylmethyl-4-(4-adamantyl-phenyl)-indenyl]zirconiumdichloride,(Methyl)(n-propyl)silanediylbis[2-bicyclo[2.2.1]heptylmethyl-4-(3-biphenyl)-indenyl]zirconiumdichloride,(Methyl)(n-propyl)silanediylbis[2-bicyclo[2.2.1]heptylmethyl-4-(3,5-dimethyl-phenyl)-indenyl]zirconiumdichloride,(Methyl)(n-propyl)silanediylbis[2-bicyclo[2.2.1]heptylmethyl-4-(3,5-di-(trifluoromethyl)-phenyl)-indenyl]zirconiumdichloride,(Methyl)(n-propyl)silanediylbis[2-bicyclo[2.2.1]heptylmethyl-4-(3,5-terphenyl)-indenyl]zirconiumdichloride,(Methyl)(3,3,3-trifluoropropyl)silanediylbis[2-t-butylmethyl-4-(1-naphthyl)-indenyl]zirconiumdichloride,(Methyl)(3,3,3-trifluoropropyl)silanediylbis[2-t-butylmethyl-4-(2-naphthyl)-indenyl]zirconiumdichloride,(Methyl)(3,3,3-trifluoropropyl)silanediylbis[2-t-butylmethyl-4-(4-methyl-phenyl)-indenyl]zirconiumdichloride,(Methyl)(3,3,3-trifluoropropyl)silanediylbis[2-t-butylmethyl-4-(4-biphenyl)-indenyl]zirconiumdichloride,(Methyl)(3,3,3-trifluoropropyl)silanediylbis[2-t-butylmethyl-4-(4-ethyl-phenyl)-indenyl]zirconiumdichloride,(Methyl)(3,3,3-trifluoropropyl)silanediylbis[2-t-butylmethyl-4-(4-n-propyl-phenyl)-indenyl]zirconiumdichloride,(Methyl)(3,3,3-trifluoropropyl)silanediylbis[2-t-butylmethyl-4-(4-i-propyl-phenyl)-indenyl]zirconiumdichloride,(Methyl)(3,3,3-trifluoropropyl)silanediylbis[2-t-butylmethyl-4-(4-t-butyl-phenyl)-indenyl]zirconiumdichloride,(Methyl)(3,3,3-trifluoropropyl)silanediylbis[2-t-butylmethyl-4-(4-sec-butyl-phenyl)-indenyl]zirconiumdichloride,(Methyl)(3,3,3-trifluoropropyl)silanediylbis[2-t-butylmethyl-4-(4-cyclohexyl-phenyl)-indenyl]zirconiumdichloride,(Methyl)(3,3,3-trifluoropropyl)silanediylbis[2-t-butylmethyl-4-(4-trimethylsilyl-phenyl)-indenyl]zirconiumdichloride,(Methyl)(3,3,3-trifluoropropyl)silanediylbis[2-t-butylmethyl-4-(4-adamantyl-phenyl)-indenyl]zirconiumdichloride,(Methyl)(3,3,3-trifluoropropyl)silanediylbis[2-t-butylmethyl-4-(3-biphenyl)-indenyl]zirconiumdichloride,(Methyl)(3,3,3-trifluoropropyl)silanediylbis[2-t-butylmethyl-4-(3,5-dimethyl-phenyl)-indenyl]zirconiumdichloride,(Methyl)(3,3,3-trifluoropropyl)silanediylbis[2-t-butylmethyl-4-(3,5-di-(trifluoromethyl)-phenyl)-indenyl]zirconiumdichloride,(Methyl)(3,3,3-trifluoropropyl)silanediylbis[2-t-butylmethyl-4-(3,5-terphenyl)-indenyl]zirconiumdichloride,(Methyl)(3,3,3-trifluoropropyl)silanediylbis[2-cyclopentylmethyl-4-(1-naphthyl)-indenyl]zirconiumdichloride,(Methyl)(3,3,3-trifluoropropyl)silanediylbis[2-cyclopentylmethyl-4-(2-naphthyl)-indenyl]zirconiumdichloride,(Methyl)(3,3,3-trifluoropropyl)silanediylbis[2-cyclopentylmethyl-4-(4-methyl-phenyl)-indenyl]zirconiumdichloride,(Methyl)(3,3,3-trifluoropropyl)silanediylbis[2-cyclopentylmethyl-4-(4-biphenyl)-indenyl]zirconiumdichloride,(Methyl)(3,3,3-trifluoropropyl)silanediylbis[2-cyclopentylmethyl-4-(4-ethyl-phenyl)-indenyl]zirconiumdichloride,(Methyl)(3,3,3-trifluoropropyl)silanediylbis[2-cyclopentylmethyl-4-(4-n-propyl-phenyl)-indenyl]zirconiumdichloride,(Methyl)(3,3,3-trifluoropropyl)silanediylbis[2-cyclopentylmethyl-4-(4-i-propyl-phenyl)-indenyl]zirconiumdichloride,(Methyl)(3,3,3-trifluoropropyl)silanediylbis[2-cyclopentylmethyl-4-(4-t-butyl-phenyl)-indenyl]zirconiumdichloride,(Methyl)(3,3,3-trifluoropropyl)silanediylbis[2-cyclopentylmethyl-4-(4-sec-butyl-phenyl)-indenyl]zirconiumdichloride,(Methyl)(3,3,3-trifluoropropyl)silanediylbis[2-cyclopentylmethyl-4-(4-cyclohexyl-phenyl)-indenyl]zirconiumdichloride,(Methyl)(3,3,3-trifluoropropyl)silanediylbis[2-cyclopentylmethyl-4-(4-trimethylsilyl-phenyl)-indenyl]zirconiumdichloride,(Methyl)(3,3,3-trifluoropropyl)silanediylbis[2-cyclopentylmethyl-4-(4-adamantyl-phenyl)-indenyl]zirconiumdichloride,(Methyl)(3,3,3-trifluoropropyl)silanediylbis[2-cyclopentylmethyl-4-(3-biphenyl)-indenyl]zirconiumdichloride,(Methyl)(3,3,3-trifluoropropyl)silanediylbis[2-cyclopentylmethyl-4-(3,5-dimethyl-phenyl)-indenyl]zirconiumdichloride,(Methyl)(3,3,3-trifluoropropyl)silanediylbis[2-cyclopentylmethyl-4-(3,5-di-(trifluoromethyl)-phenyl)-indenyl]zirconiumdichloride,(Methyl)(3,3,3-trifluoropropyl)silanediylbis[2-cyclopentylmethyl-4-(3,5-terphenyl)-indenyl]zirconiumdichloride,(Methyl)(3,3,3-trifluoropropyl)silanediylbis[2-cyclohexylmethyl-4-(1-naphthyl)-indenyl]zirconiumdichloride,(Methyl)(3,3,3-trifluoropropyl)silanediylbis[2-cyclohexylmethyl-4-(2-naphthyl)-indenyl]zirconiumdichloride,(Methyl)(3,3,3-trifluoropropyl)silanediylbis[2-cyclohexylmethyl-4-(4-methyl-phenyl)-indenyl]zirconiumdichloride,(Methyl)(3,3,3-trifluoropropyl)silanediylbis[2-cyclohexylmethyl-4-(4-biphenyl)-indenyl]zirconiumdichloride,(Methyl)(3,3,3-trifluoropropyl)silanediylbis[2-cyclohexylmethyl-4-(4-ethyl-phenyl)-indenyl]zirconiumdichloride,(Methyl)(3,3,3-trifluoropropyl)silanediylbis[2-cyclohexylmethyl-4-(4-n-propyl-phenyl)-indenyl]zirconiumdichloride,(Methyl)(3,3,3-trifluoropropyl)silanediylbis[2-cyclohexylmethyl-4-(4-i-propyl-phenyl)-indenyl]zirconiumdichloride,(Methyl)(3,3,3-trifluoropropyl)silanediylbis[2-cyclohexylmethyl-4-(4-t-butyl-phenyl)-indenyl]zirconiumdichloride,(Methyl)(3,3,3-trifluoropropyl)silanediylbis[2-cyclohexylmethyl-4-(4-sec-butyl-phenyl)-indenyl]zirconiumdichloride,(Methyl)(3,3,3-trifluoropropyl)silanediylbis[2-cyclohexylmethyl-4-(4-cyclohexyl-phenyl)-indenyl]zirconiumdichloride,(Methyl)(3,3,3-trifluoropropyl)silanediylbis[2-cyclohexylmethyl-4-(4-trimethylsilyl-phenyl)-indenyl]zirconiumdichloride,(Methyl)(3,3,3-trifluoropropyl)silanediylbis[2-cyclohexylmethyl-4-(4-adamantyl-phenyl)-indenyl]zirconiumdichloride,(Methyl)(3,3,3-trifluoropropyl)silanediylbis[2-cyclohexylmethyl-4-(3-biphenyl)-indenyl]zirconiumdichloride,(Methyl)(3,3,3-trifluoropropyl)silanediylbis[2-cyclohexylmethyl-4-(3,5-dimethyl-phenyl)-indenyl]zirconiumdichloride,(Methyl)(3,3,3-trifluoropropyl)silanediylbis[2-cyclohexylmethyl-4-(3,5-di-(trifluoromethyl)-phenyl)-indenyl]zirconiumdichloride,(Methyl)(3,3,3-trifluoropropyl)silanediylbis[2-cyclohexylmethyl-4-(3,5-terphenyl)-indenyl]zirconiumdichloride,(Methyl)(3,3,3-trifluoropropyl)silanediylbis[2-cycloheptylmethyl-4-(1-naphthyl)-indenyl]zirconiumdichloride,(Methyl)(3,3,3-trifluoropropyl)silanediylbis[2-cycloheptylmethyl-4-(2-naphthyl)-indenyl]zirconiumdichloride,(Methyl)(3,3,3-trifluoropropyl)silanediylbis[2-cycloheptylmethyl-4-(4-methyl-phenyl)-indenyl]zirconiumdichloride,(Methyl)(3,3,3-trifluoropropyl)silanediylbis[2-cycloheptylmethyl-4-(4-biphenyl)-indenyl]zirconiumdichloride,(Methyl)(3,3,3-trifluoropropyl)silanediylbis[2-cycloheptylmethyl-4-(4-ethyl-phenyl)-indenyl]zirconiumdichloride,(Methyl)(3,3,3-trifluoropropyl)silanediylbis[2-cycloheptylmethyl-4-(4-n-propyl-phenyl)-indenyl]zirconiumdichloride,(Methyl)(3,3,3-trifluoropropyl)silanediylbis[2-cycloheptylmethyl-4-(4-i-propyl-phenyl)-indenyl]zirconiumdichloride,(Methyl)(3,3,3-trifluoropropyl)silanediylbis[2-cycloheptylmethyl-4-(4-t-butyl-phenyl)-indenyl]zirconiumdichloride,(Methyl)(3,3,3-trifluoropropyl)silanediylbis[2-cycloheptylmethyl-4-(4-sec-butyl-phenyl)-indenyl]zirconiumdichloride,(Methyl)(3,3,3-trifluoropropyl)silanediylbis[2-cycloheptylmethyl-4-(4-cyclohexyl-phenyl)-indenyl]zirconiumdichloride,(Methyl)(3,3,3-trifluoropropyl)silanediylbis[2-cycloheptylmethyl-4-(4-trimethylsilyl-phenyl)-indenyl]zirconiumdichloride,(Methyl)(3,3,3-trifluoropropyl)silanediylbis[2-cycloheptylmethyl-4-(4-adamantyl-phenyl)-indenyl]zirconiumdichloride,(Methyl)(3,3,3-trifluoropropyl)silanediylbis[2-cycloheptylmethyl-4-(3-biphenyl)-indenyl]zirconiumdichloride,(Methyl)(3,3,3-trifluoropropyl)silanediylbis[2-cycloheptylmethyl-4-(3,5-dimethyl-phenyl)-indenyl]zirconiumdichloride,(Methyl)(3,3,3-trifluoropropyl)silanediylbis[2-cycloheptylmethyl-4-(3,5-di-(trifluoromethyl)-phenyl)-indenyl]zirconiumdichloride,(Methyl)(3,3,3-trifluoropropyl)silanediylbis[2-cycloheptylmethyl-4-(3,5-terphenyl)-indenyl]zirconiumdichloride,(Methyl)(3,3,3-trifluoropropyl)silanediylbis[2-adamantylmethyl-4-(1-naphthyl)-indenyl]zirconiumdichloride,(Methyl)(3,3,3-trifluoropropyl)silanediylbis[2-adamantylmethyl-4-(2-naphthyl)-indenyl]zirconiumdichloride,(Methyl)(3,3,3-trifluoropropyl)silanediylbis[2-adamantylmethyl-4-(4-methyl-phenyl)-indenyl]zirconiumdichloride,(Methyl)(3,3,3-trifluoropropyl)silanediylbis[2-adamantylmethyl-4-(4-biphenyl)-indenyl]zirconiumdichloride,(Methyl)(3,3,3-trifluoropropyl)silanediylbis[2-adamantylmethyl-4-(4-ethyl-phenyl)-indenyl]zirconiumdichloride,(Methyl)(3,3,3-trifluoropropyl)silanediylbis[2-adamantylmethyl-4-(4-n-propyl-phenyl)-indenyl]zirconiumdichloride,(Methyl)(3,3,3-trifluoropropyl)silanediylbis[2-adamantylmethyl-4-(4-i-propyl-phenyl)-indenyl]zirconiumdichloride,(Methyl)(3,3,3-trifluoropropyl)silanediylbis[2-adamantylmethyl-4-(4-t-butyl-phenyl)-indenyl]zirconiumdichloride,(Methyl)(3,3,3-trifluoropropyl)silanediylbis[2-adamantylmethyl-4-(4-sec-butyl-phenyl)-indenyl]zirconiumdichloride,(Methyl)(3,3,3-trifluoropropyl)silanediylbis[2-adamantylmethyl-4-(4-cyclohexyl-phenyl)-indenyl]zirconiumdichloride,(Methyl)(3,3,3-trifluoropropyl)silanediylbis[2-adamantylmethyl-4-(4-trimethylsilyl-phenyl)-indenyl]zirconiumdichloride,(Methyl)(3,3,3-trifluoropropyl)silanediylbis[2-adamantylmethyl-4-(4-adamantyl-phenyl)-indenyl]zirconiumdichloride,(Methyl)(3,3,3-trifluoropropyl)silanediylbis[2-adamantylmethyl-4-(3-biphenyl)-indenyl]zirconiumdichloride,(Methyl)(3,3,3-trifluoropropyl)silanediylbis[2-adamantylmethyl-4-(3,5-dimethyl-phenyl)-indenyl]zirconiumdichloride,(Methyl)(3,3,3-trifluoropropyl)silanediylbis[2-adamantylmethyl-4-(3,5-di-(trifluoromethyl)-phenyl)-indenyl]zirconiumdichloride,(Methyl)(3,3,3-trifluoropropyl)silanediylbis[2-adamantylmethyl-4-(3,5-terphenyl)-indenyl]zirconiumdichloride,(Methyl)(3,3,3-trifluoropropyl)silanediylbis[2-bicyclo[2.2.1]heptylmethyl-4-(1-naphthyl)-indenyl]zirconiumdichloride,(Methyl)(3,3,3-trifluoropropyl)silanediylbis[2-bicyclo[2.2.1]heptylmethyl-4-(2-naphthyl)-indenyl]zirconiumdichloride,(Methyl)(3,3,3-trifluoropropyl)silanediylbis[2-bicyclo[2.2.1]heptylmethyl-4-(4-methyl-phenyl)-indenyl]zirconiumdichloride,(Methyl)(3,3,3-trifluoropropyl)silanediylbis[2-bicyclo[2.2.1]heptylmethyl-4-(4-biphenyl)-indenyl]zirconiumdichloride,(Methyl)(3,3,3-trifluoropropyl)silanediylbis[2-bicyclo[2.2.1]heptylmethyl-4-(4-ethyl-phenyl)-indenyl]zirconiumdichloride,(Methyl)(3,3,3-trifluoropropyl)silanediylbis[2-bicyclo[2.2.1]heptylmethyl-4-(4-n-propyl-phenyl)-indenyl]zirconiumdichloride,(Methyl)(3,3,3-trifluoropropyl)silanediylbis[2-bicyclo[2.2.1]heptylmethyl-4-(4-i-propyl-phenyl)-indenyl]zirconiumdichloride,(Methyl)(3,3,3-trifluoropropyl)silanediylbis[2-bicyclo[2.2.1]heptylmethyl-4-(4-t-butyl-phenyl)-indenyl]zirconiumdichloride,(Methyl)(3,3,3-trifluoropropyl)silanediylbis[2-bicyclo[2.2.1]heptylmethyl-4-(4-sec-butyl-phenyl)-indenyl]zirconiumdichloride,(Methyl)(3,3,3-trifluoropropyl)silanediylbis[2-bicyclo[2.2.1]heptylmethyl-4-(4-cyclohexyl-phenyl)-indenyl]zirconiumdichloride,(Methyl)(3,3,3-trifluoropropyl)silanediylbis[2-bicyclo[2.2.1]heptylmethyl-4-(4-trimethylsilyl-phenyl)-indenyl]zirconiumdichloride,(Methyl)(3,3,3-trifluoropropyl)silanediylbis[2-bicyclo[2.2.1]heptylmethyl-4-(4-adamantyl-phenyl)-indenyl]zirconiumdichloride,(Methyl)(3,3,3-trifluoropropyl)silanediylbis[2-bicyclo[2.2.1]heptylmethyl-4-(3-biphenyl)-indenyl]zirconiumdichloride,(Methyl)(3,3,3-trifluoropropyl)silanediylbis[2-bicyclo[2.2.1]heptylmethyl-4-(3,5-dimethyl-phenyl)-indenyl]zirconiumdichloride,(Methyl)(3,3,3-trifluoropropyl)silanediylbis[2-bicyclo[2.2.1]heptylmethyl-4-(3,5-di-(trifluoromethyl)-phenyl)-indenyl]zirconiumdichloride,(Methyl)(3,3,3-trifluoropropyl)silanediylbis[2-bicyclo[2.2.1]heptylmethyl-4-(3,5-terphenyl)-indenyl]zirconiumdichloride,Dimethylsilanediylbis[2-cyclohexylmethyl-4-(1-naphthyl)-6-methylindenyl]zirconiumdichloride,Dimethylsilanediylbis[2-cyclohexylmethyl-4-(2-naphthyl)-6-methylindenyl]zirconiumdichloride,Dimethylsilanediylbis[2-cyclohexylmethyl-4-(4-methyl-phenyl)-6-methylindenyl]zirconiumdichloride,Dimethylsilanediylbis[2-cyclohexylmethyl-4-(4-biphenyl)-6-methylindenyl]zirconiumdichloride,Dimethylsilanediylbis[2-cyclohexylmethyl-4-(4-ethyl-phenyl)-6-methylindenyl]zirconiumdichloride,Dimethylsilanediylbis[2-cyclohexylmethyl-4-(4-n-propyl-phenyl)-6-methylindenyl]zirconiumdichloride,Dimethylsilanediylbis[2-cyclohexylmethyl-4-(4-i-propyl-phenyl)-6-methylindenyl]zirconiumdichloride,Dimethylsilanediylbis[2-cyclohexylmethyl-4-(4-t-butyl-phenyl)-6-methylindenyl]zirconiumdichloride,Dimethylsilanediylbis[2-cyclohexylmethyl-4-(4-sec-butyl-phenyl)-6-methylindenyl]zirconiumdichloride,Dimethylsilanediylbis[2-cyclohexylmethyl-4-(4-cyclohexyl-phenyl)-6-methylindenyl]zirconiumdichloride,Dimethylsilanediylbis[2-cyclohexylmethyl-4-(4-trimethylsilyl-phenyl)-6-methylindenyl]zirconiumdichloride,Dimethylsilanediylbis[2-cyclohexylmethyl-4-(4-adamantyl-phenyl)-6-methylindenyl]zirconiumdichloride,Dimethylsilanediylbis[2-cyclohexylmethyl-4-(3-biphenyl)-6-methylindenyl]zirconiumdichloride,Dimethylsilanediylbis[2-cyclohexylmethyl-4-(3,5-dimethyl-phenyl)-6-methylindenyl]zirconiumdichloride,Dimethylsilanediylbis[2-cyclohexylmethyl-4-(3,5-di-(trifluoromethyl)-phenyl)-6-methylindenyl]zirconiumdichloride,Dimethylsilanediylbis[2-cyclohexylmethyl-4-(3,5-terphenyl)-6-methylindenyl]zirconiumdichloride,Dimethylsilanediylbis[2-cyclohexylmethyl-4-(1-naphthyl)-7-methylindenyl]zirconiumdichloride,Dimethylsilanediylbis[2-cyclohexylmethyl-4-(2-naphthyl)-7-methylindenyl]zirconiumdichloride,Dimethylsilanediylbis[2-cyclohexylmethyl-4-(4-methyl-phenyl)-7-methylindenyl]zirconiumdichloride,Dimethylsilanediylbis[2-cyclohexylmethyl-4-(4-biphenyl)-7-methylindenyl]zirconiumdichloride,Dimethylsilanediylbis[2-cyclohexylmethyl-4-(4-ethyl-phenyl)-7-methylindenyl]zirconiumdichloride,Dimethylsilanediylbis[2-cyclohexylmethyl-4-(4-n-propyl-phenyl)-7-methylindenyl]zirconiumdichloride,Dimethylsilanediylbis[2-cyclohexylmethyl-4-(4-i-propyl-phenyl)-7-methylindenyl]zirconiumdichloride,Dimethylsilanediylbis[2-cyclohexylmethyl-4-(4-t-butyl-phenyl)-7-methylindenyl]zirconiumdichloride,Dimethylsilanediylbis[2-cyclohexylmethyl-4-(4-sec-butyl-phenyl)-7-methylindenyl]zirconiumdichloride,Dimethylsilanediylbis[2-cyclohexylmethyl-4-(4-cyclohexyl-phenyl)-7-methylindenyl]zirconiumdichloride,Dimethylsilanediylbis[2-cyclohexylmethyl-4-(4-trimethylsilyl-phenyl)-7-methylindenyl]zirconiumdichloride,Dimethylsilanediylbis[2-cyclohexylmethyl-4-(4-adamantyl-phenyl)-7-methylindenyl]zirconiumdichloride,Dimethylsilanediylbis[2-cyclohexylmethyl-4-(3-biphenyl)-7-methylindenyl]zirconiumdichloride,Dimethylsilanediylbis[2-cyclohexylmethyl-4-(3,5-dimethyl-phenyl)-7-methylindenyl]zirconiumdichloride,Dimethylsilanediylbis[2-cyclohexylmethyl-4-(3,5-di-(trifluoromethyl)-phenyl)-7-methylindenyl]zirconiumdichlorideandDimethylsilanediylbis[2-cyclohexylmethyl-4-(3,5-terphenyl)-7-methylindenyl]zirconiumdichloride.61. A process for olefin polymerisation comprising contacting one ormore olefins each having from 2 to about 20 carbon atoms under olefinpolymerisation reaction conditions with a catalyst system including abridged metallocene component according to claim
 52. 62. The process ofclaim 61 wherein the olefins include propylene and/or ethylene.
 63. Theprocess of claim 61 wherein the olefins include at least one olefinhaving the formula R^(m)—CH═CH—R^(n) wherein R^(m) and R^(n) can beidentical or different and are each individually a hydrogen atom or aradical having from 1 to about 20 carbon atoms, or R^(m) and R^(n)together can form one or more rings.
 64. The process of claim 61 whereinthe olefins include one or more compounds selected from the groupconsisting of ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 4methyl-1-pentene or 1-octene, styrene, 1,3-butadiene, 1,4-hexadiene,vinylnorbornene, norbornadiene, ethylnorbornadiene, norbornene,tetracyclododecene and methylnorbornene.